US3148154A - Prevention and/or resolution of emulsions - Google Patents
Prevention and/or resolution of emulsions Download PDFInfo
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- US3148154A US3148154A US28514A US2851460A US3148154A US 3148154 A US3148154 A US 3148154A US 28514 A US28514 A US 28514A US 2851460 A US2851460 A US 2851460A US 3148154 A US3148154 A US 3148154A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G33/00—Dewatering or demulsification of hydrocarbon oils
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S507/00—Earth boring, well treating, and oil field chemistry
- Y10S507/921—Specified breaker component for emulsion or gel
Definitions
- methylol phenol is not preformed but is formed in the presence of the polyamine, or the preformed methylol phenol is condensed with the polyamine in the presence of an extraneous catalyst, either acidic or basic, for example, basic or alkaline materials such as NaOH, Ca(OH) Na CO sodium methylate, etc.
- an extraneous catalyst either acidic or basic, for example, basic or alkaline materials such as NaOH, Ca(OH) Na CO sodium methylate, etc.
- a polymeric product is formed.
- a polymeric product is also produced.
- less than one mole of secondary amine is reacted per equivalent of methylol group, a polymeric product is also formed.
- Patented Sept. 8, 1964 preferably at to C.
- Water can be removed by any suitable means, for example, by use of an azeotroping agent, reduced pressure, combinations thereof, etc. Measuring the water given olf during the reaction is a convenient method of judging completion of the reaction.
- Monophenols.-A phenol containing 1, 2 or 3 methylol groups in the ortho or para position i.e. the 2, 4, 6 positions
- the remaining positions on the ring containing hydrogen or groups which do not interfere with the polyamine-methylol group condensation, for example, alkyl, alkenyl, cycloalkyl, phenyl, halogen, and alkoxy, etc., groups, and having but one nuclear linked hydroxyl group.
- Diphen0ls.-One type is a diphenol containing two hydroxybenzene radicals directly joined together through the ortho or para (i.e. 2, 4 or 6) position with a bond joining the carbon of one ring with the carbon of the other ring, each hydroxybenzene radical containing 1 to 2 methylol groups in the 2, 4 or 6 positions, the remaining positions on each ring containing hydrogen or groups which do not interfere with the polyamine-methylol group condensation, for example, alkyl, alkenyl, cycloalkyl, phenyl, halogen, alkoxy, etc., groups, and having but two nuclear linked hydroxyl groups.
- a second type is a diphenol containing two hydroxybenzene radicals joined together through the ortho or para (i.e. 2, 4 or 6 position with a bridge joining the carbon of one ring to a carbon of the other ring, said bridge being, for example, alkylene, alkylidene, oxygen, carbonyl, sulfur, sulfoxide and sulfone, etc., each hydroxybenzene radical containing 1 to 2 methylol groups in the 2, 4 or 6 positions, the remaining positions on each ring containing hydrogen or groups which do not interfere with the polyaminomethylol group condensation, for example, alkyl, alkenyl, cycloalkyl, phenyl, halogen, alkoxy, etc., groups, and having but two nuclear linked hydroxyl groups.
- the Rs contains an amino group and the Rs contain alkyl, alkoxy, cycloalkyl, aryl, aralkyl, alkaryl, radicals and the corresponding radicals containing heterocyclic radicals, hydroxy radicals, etc.
- the Rs may also be joined together to form heterocyclic polyarnines.
- the preferred classes of polyamines are the alkylene polyamines, the hydroxylated alkylene polyamines, branched polyamines containing at least three primary amino groups, and polyamines containing cyclic amidine groups. The only limitation is that there shall be present in the polyamine at least one secondary amino group which is not bonded directly to a negative radical which reduces the basicity of the amine, such as a phenyl group.
- An unusual feature of the products employed in the process of the present invention is the discovery that methylol phenols react more readily under the herein specified conditions with secondary amino groups than with primary amino groups. Thus, where both primary and secondary amino groups are present in the same molecule, reaction occurs more readily with the secondary amino group. However, where the polyarnine contains only primary amino groups, the product formed under reaction conditions as mentioned above is an insoluble resin. In contrast, where the same number of primary amino groups are present on the amine in addition to at least one secondary amino group, reaction occurs predominantly with the secondary amino group to form nonresinous derivatives. Thus, where trimethylol phenol is reacted with ethylene diamine, an insoluble resinous composition is produced. However, where diethylene triamine, a compound having just as many primary amino groups as ethylene diamine, is reacted, according to this invention a non-resinous product is unexpectedly formed.
- monomeric refers to a polyaminomethylphenol containing Within the molecular unit one aromatic unit corresponding to the aromatic unit derived from the starting methylol phenol and one polyamine unit for each methylol group originally in the phenol. This is in contrast to a polymeric or resinous polyaminomethyl phenol containing within the molecular unit more than one aromatic unit and/ or more than one polyamino unit for each methylol group.
- A is the aromatic unit corresponding to that of the methylol reactant, and the remainder of the molecule is the polyaminomet'nyl radical, one for each of the original methylol groups.
- the molar ratio of alkylene oxide to amine condensate can range within wide limits, for example, from a 1:1 mole ratio to a ratio of 1000zl, or higher, but preferably 1 to 200.
- extremely high alkylene oxide ratios are advantageously employed such as 200-300 or more pounds of alkylene oxide per pound of amine condensate.
- desired hydrophilic or hydrophobic properties are imparted to the composition.
- oxyalkylation reactions are conducted under a wide variety of conditions, at low or high pressures, at low or high temperatures, in the presence or absence of catalyst, solvent, etc.
- oxyalkylation reactions can be carried out at temperatures of from 80-200 C., and pressures of from to 200 p.s.i., and times of from min. to several days. Preferably oxyalkylation reactions are carried out at 80 to 120 C. and 10 to 30 psi.
- oxyalkylation reactions see U.S. Patent 2,792,369 and other patents mentioned therein.
- acylation is conducted at a temperature suificiently high to eliminate water and below the pyrolytic point of the reactants and the reaction products.
- the reaction is carried out at a temperature of from 140 to 280 C., but preferably at 140 to 200 C.
- acylating one should control the reaction so that the phenolic hydroxyls are not acylated. Because acyl halides and anhydrides are capable of reacting with phenolic hydroxyls, this type of acylation should be avoided. It should be realized that either oxyalkylation or acylation can be employed alone or each alternately, either one preceding the other.
- the amine condensate can be acylated, then oxyalkylated and then reacylated. The amount of acylation agent reacted will depend on reactive groups or the compounds and properties desired in the final product, for example,
- non-hydroxylated amine contains a plurality of secondary amino groups, wherein one or more is susceptible to oxyalkylation, or primary amino groups, oxyalkylation may occur in those positions.
- oxyalkylation may take place not only at the phenolic hydroxyl group but also at one or more of the available amino groups.
- the amine condensate is hydroxyalkylated, this latter group furnishes an additional position of oxyalkylation susceptibility.
- the product formed in acylation will vary with the particular polyaminomethyl phenol employed. It may be an ester or an amide depending on the available reactive groups. If, however, after forming the amide at a temperature between 250 C., but usually not above 200 C., one heats such products at a higher range, approximately 250-280 C., or higher, possibly up to 300 C. for a suitable period of time, for example, 1-2 hours or longer, one can in many cases recover a second mole of water for each mole of carboxylic acid employed, the first mole of water being evolved during amidification.
- the product formed in such cases is believed to contain a cyclic amidine ring such as an imidazoline or a tetrahydropyrimidine ring.
- compositions contain basic nitrogen groups, they are capable of reacting with inorganic acids, for example hydrohalogens (HCl, HBr, HI), sulfuric acid, phosphoric acid, etc., aliphatic acids (acetic, propionic, glycolic, diglycolic, etc.), aromatic acids (benzoic, salicylic, phthalic, etc.), and organic compounds capable of forming salts, for example, those having the general formula RX wherein R is an organic group, such as an alkyl group (e.g.
- X is a radical capable of forming a salt such as those derived from acids (e.g. halide, sulfate, phosphate, sulfonates, etc., radicals).
- N comprises the part of the compound containing the nitrogen group which has been rendered positively charged by the H or R of the alkylating compound and X represents the anion derived from the alkylating compound.
- R is an aliphatic saturated or unsaturated hydrocarbon having, for example, 1-30 carbon atoms, for example, methyl, ethyl, propyl, butyl, sec-butyl, tertbutyl, amyl, tert-amyl, hexyl, tert-hexyl, octyl, nonyl, decyl, dodecyl, octo-decyl, etc., the corresponding unsaturated groups, etc.
- One species is are diphenol species advantageously GH2OH CH OH If I CHzOH CHzOH where R is hydrogen or a lower alkyl, preferably methyl.
- a second species is where R has the same meaning as that of the second species of the monophenols and R is hydrogen or a lower alkyl, preferably methyl.
- polyamine 1s R HN/ the general formula for the polyamine 1s R HN/ This indicates that a wide variety of reactive secondary polyamines can be employed, including aliphatic polyamines, cycloaliphatic polyamines, aromatic polyamines (provided the aromatic polyamine has at least one secondary amine which has no negative group, such as a phenyl group directly bonded thereto) heterocyclic polyamines and polyamines containing mixtures of the above groups.
- the term polyamine includes compounds having one amino group on one kind of radical, for example, an aliphatic radical, and another amino group on the heterocyclic radical as in the case of the following formula:
- the polyamine has at least one secondary amino group capable of condensing with the methylol group. It also includes compounds which are totally heterocyclic, having a similarly reactive secondary amino group. It also includes polyamines having other elements besides carbon, hydrogen and nitrogen, for example, those also containing oxygen, sulfur, etc.
- the preferred embodiments of the present invention are the alkylene polyamines, the hydroxylated alkylene polyamines and the amino cyclic amidines.
- Polyamines are available commercially and can be prepared by well-known methods. It is well known that olefin dichlorides, particularly those containing from 2 to 10 carbon atoms, can be reacted with ammonia or amines to give alkylene polyarnines. If, instead of using ethylene dichloride, the corresponding propylene, butylene, amylene or higher molecular weight dichlorides are used, one then obtains the comparable homologues. One can also alpha-omega dialkyl ethers such as CICH OCH CI; ClCH CH OCH CH Cl, and the like. Such polyamines can be alkylated in the manner commonly employed for alkylating monoarnines.
- Alkylation is not limited to the introduction of an alkyl group, but as a matter of fact, the radical introduced can be characterized by a carbon atom chain interrupted at least once by an oxygen atom.
- alkylation is accomplished by compounds which are essentially alkyoxyalkyl chlorides, as, for example, the following:
- any suitable polyalkylene polyamine such as an ethylene polyamine, a propylene polyamine, etc., treated with ethylene oxide or similar oxyalkylating agent are useful.
- various hydroxylated amines such as monoethanolamine, monopropanolamine, and the like, are also treated with a suitable alkylene dichloride, such as ethylene dichloride, propylene dichloride, etc.
- Such reactions are entirely comparable to the alkylation reaction involving alkyl chlorides previously described.
- Other reactions involve the use of an alkylene oxide, such as ethylene oxide, propylene oxide, butylene oxide, octylene oxide, styrene oxide or the like.
- Glycide is advantageously employed.
- the type of reaction just referred to is well known and results in the introduction of a hydroxylated or polyhydroxylated' radical in an amino hydrogen position. It is also possible to introduce a hydroxylated oxyhydrocarbon atom; for instance, instead of using the chlorhydn'n corresponding to ethylene glycol, one employs the chlorhydrin corresponding to diethylene glycol. Similarly, instead of using the chlorhydrin corresponding to glycerol, one employs the chlorhydrin corresponding to diglycerol.
- R x R which are the same or different, comprise hydrogen, alkyl, cycloalkyl, aryl, alkyloxyalkyl, hydroxylated alkyl, hydroxylated alkyloxyalkyl, etc, radicals, x is zero or a whole number of at least one, for example 1 to 10, but preferably 1 to 3, provided the polyamine contains at least one secondary amino group, and n is a whole number, 2 or greater, for example 210, but preferably 2-5.
- a particularly useful class of polyamines is a class of branched polyamines.
- These branched polyamines are polyalkylene polyamines wherein the branched group is a side chain containing on the average at least one nitrogenbonded aminoalkylene anna s group per nine amino units present on the main chain, for example 14 of such branched chains per nine units on the main chain, but preferably one side chain unit per nine main chain units.
- these polyamines contain at least three primary amino groups and at least one tertiary amino group in addition to at least one secondary amino group.
- R is an alkylene group such as ethylene, propylene, butylene. and other homologues (both straight chained and branched), etc., but preferably ethylene; and x, y and z are integers, x being for'exarnple, from 4 to 24 or more but preferably 6 to 18, y being for example 1 to 6 or more but preferably 1 to 3, and z being for example 0-6 but preferably 0-1.
- the x and y units may be sequential, alternative, orderly or randomly distributed.
- the preferred class of branched polyamines includes those of the formula formula l I l R I IH 11 where n is an integer, for example 1-20 or more but preferably 1-3, wherein R is preferably ethylene, but may be propylene, butylene, etc. (straight chained or branched).
- brackets may be joined in a headto-head or a head-to-tail fashion.
- Compounds described by this formula wherein n: 1-3 are manufactured and sold by Dow Chemical Company as Polyamines N400, N-800, N-1200, etc.
- the branched polyamines can be prepared by a wide variety of methods.
- One method comprises the reaction of ethanolamine and ammonia under pressure over a fixed bed of a metal hydrogenation catalyst. By controlling the conditions of this reaction one can obtain various amounts of piperazine and polyamines as well as the branched chain polyalkylene polyamine. This process is described in Australian Patent No. 42,189 and in the East German Patent 14,480 (March 17, 1958) reported in Chem. Abstracts, August 10, 1958, 14129.
- the branched nature of the polyamine imparts unusual properties to the polyamine and its derivatives.
- Cyclic aliphatic polyamines having at least one secondary amino group such as piperazine, etc., can also be employed.
- Suitable polyamines also include polyamines wherein the alkylene group or groups are interrupted by an oxygen radical, for example,
- R R R R where R, n and x has the meaning previously stated for the linear polyamine.
- the polyamine has where R is alkyl and Z is an alkylene group containing phenyl groups on some of the alkylene radicals since the phenyl group is not attached directly to the secondary amino group.
- alkylene group substituted with a hydroxy group OH H is reactive.
- the following general procedure is employed in preparing the polyamine-methylol condensate.
- the methylolphenol is generally mixed or slowly added to the polyamine in ratios of 1 mole of polyamine per equivalent of methylol group on the phenol.
- addition is carried out below 60 C. until at least one mole of polyamine per methylol group has been added.
- Enough of a suitable azeotroping agent is then added to remove water (benzene, toluene, or xylene) and heat applied. After removal of the calculated amount of water from the reaction mixture (one mole of water per equivalent of methylol group) heating is stopped and the azeotroping agent is evaporated off under vacuum.
- Example 28a This example illustrates. the reaction of a methylolmonophenol and a branched polyamine.
- a one liter flask is employed equipped with a conventional stirring device, thermometer, phase separating trap, condenser, heating mantle, etc.
- Polyamine N-400 200 grams (0.50 mole) is placed in the flask and mixed with 150 grams of xylene.
- To this stirred mixture is added dropwise over a period of 15 minutes 44.0 grams (0.17 mole) of a 70% aqueous solution of 2,4,6-trimethylol phenol. There is no apparent temperature change.
- the reaction mixture is then heated to C., refluxed 45 minutes, and 24 milliliters of water is collected (the calculated amount of water is 22 milliliters).
- the product is a dark brown liquid (as a 68% xylene solution).
- Example 5 b In this example, 1 mole of substantially water-free is reacted with 2 moles of Duomeen S (Armour Co.),
- R is a fatty group derived from soya oil, in the manner of Example 2a.
- Xylene is used as both solvent and azeotroping agent.
- the reaction time is 8 hours and the maximum temperature ISO-160 C.
- the polyamine-methylol condensate will have a basic number, for example, 1a, 4b, 6c, 4d, wherein those in the A series are derived from TMP, the B series from DMP, the C series from trimethylol cardanol and side chain hydrogenated cardanol (i.e., hydrocardanol), and the d series from the tetramethylol diphenols.
- the basic number always refers to the same amino condensate.
- the symbol A before the basic number indicates that the polyamine had been acylated prior to condensation.
- the symbol A after the basic number indicates that acylation takes place after condensation.
- acylation is also carried out under dehydrating conditions, i.e., water is removed. Any of the well-known methods of acylation can be employed. For example, heat alone, heat and reduced pressure, heat in combination with an azeotroping agent, etc., are all satisfactory.
- acylating agents can be employed. However, strong acylating agents such as acyl halides, or acid anhydrides should be avoided since they are capable of esterifying phenolic hydroxy groups, a feature which is undesirable.
- Suitable acids include straight chain and branched chain, saturated and unsaturated, aliphatic, alicyclic, fatty, aromatic, hydroaroinatic, and aralkyl acids, etc.
- saturated aliphatic monocarboxylic acids are acetic, propionic, butyric, valeric, caproic, heptanoic, caprylic, nonanoic, capric, undecanoic, lauric, tridecanoic, myristic, pentadecanoic, palmitic, heptadecanoic, stearic, nonadecanoic, eicosanoic, heneicosanoic, docosanoic, tricosanoic, tetracosanoic, pentacosanoic, cerotic, heptacosanoic, montanic, nonacosanoic, melissic and the like.
- ethylenic unsaturated aliphatic acids are acrylic, methacrylic, crotonic, angelic, tiglic, the pentenoic acids, the hexenoic acids, for example, hydrosorbic acid, the heptenoic acids, the octenoic acids, the nonenoic acids,
- the decenoic acids for example, obtusilic acid, the undecenoic acids, the dodccenoic acids, for example, lauroleic, linderic, etc.
- the tridecenoic acids for example, myristoleic acid
- the pentadecenoic acids for example, the hexadecenoic acids, for example, palmitcleic acid, the heptadecenoic acids, the octodecenoic acids, for example, petrosilenic acid, oleic acid, elardic acid
- the nonadecenoic acids for example, the eicosenoic acids, the docosenoic acids, for example, erucic acid, brassidic acid, cetoleic acid, the tetracosenoic acids, and the like.
- dienoic acids examples include the pentadienoic acids, the hexadienoic acids, for example, sorbic acid, the octadienoic acids, for example, linoleic, and the like.
- trienoic acids examples include the octadecatrienoic acids, for example, linolenic acid, eleostearic acid, pseudoeleostearic acid, and the like.
- Carboxylic acids containing functional groups such as hydroxy groups can be employed. Hydroxy acids, particularly the alpha hydroxy acids include glycolic acid, lactic acid, the hydroxyvaleric acids, the hydroxy caproic acids, the hydroxyheptanoic acids, the hydroxy caprylic acids, the hydroxynonanoic acids, the hydroxycapric acids, the hydroxydecanoic acids, the hydroxy lauric acids, the hydroxy tridecanoic acids, the hydroxymyristic acids, the hydroxypentadecanoic acids, the hydroxypalmitic acids, the hydroxyhexadecanoic acids, the hydroxyheptadecanoic acids, the hydroxy stearic acids, the hydroxyoctadecenoic acids, for example, ricinoleic acid, ricinelardic acid, hydroxyoctadecenoic acids, for example, ricinstearolic acid, the hydroxyeicosanoic acids, for example, bydroxyarachidic
- acetylated hydroxyacids examples include ricinoleyl lactic acid, acetyl ricinoleic acid, chloroacetyl ricinoleic acid, and the like.
- aromatic monocarboxylic acids examples include bcnzoic acid, substituted benzoic acids, for example, the toluic acids, the xylenic acids, alkoxy benzoic acid, phenyl benzoic acid, naphthalene carboxylic acid, and the like.
- Suitable acids include phenylstearic acid, benzoyi nonylic acid, cetyloxybut ric acid, cetyloxyacetic acid, chlorstearic acid, etc.
- polycarboxylic acids examples include those of the aliphatic series, for example, oxalic, malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic, nonanedicarboxylic acid, decanedicarboxylic acids, undecanedicarboxylic acids, and the like.
- unsaturated aliphatic polycarboxylic acids 22 are fumaric, maleic, mesacenic, citraconic, glutaconic, itaconic, muconic, aconitic acids, and the like.
- aromatic polycarboxylic acids examples include phthalic, isophthalic acids, terephthalic acids, substituted derivatives thereof (e.g. alkyl, chloro, alkoxy, etc. derivatives), biphenyldicarboxylic acid, diphenylether dicarboxylic acids, diphenylsulione dicarboxylic acids and the like.
- Higher aromatic polycarboxylic acids containing more than two carboxylic groups are hemirnellitic, trimellitic, trimesic, mellophanic, prehnitic, pyromellitic acids, mellitic acid, and the like.
- acid precursors such as esters, glyccrides, etc. can be employed in place of the tree acid.
- Example 7aA The reaction product of Example 7a (TMP and oxyethylated Duomeen S) is reacted with palmitic acid in the manner of Example 311A. A xylene soluble product is formed.
- Example 28aA Into a 300 milliliter flask, fitted with a stirring device,
- thermometer, phase separating trap, condenser and heating mantle is placed a xylene solution of the product of Example 28a containing 98.0 grams (0.05 mole) of the reaction product of 2,4,6-trimethylolphenol and Polyamine N400 and about 24 grams of xylene. To this. solution is added with stirring 30.0 grams (0.15 mole) of lauric acid. The reaction mixture is heated for about one hour at a maximum reaction temperature of 190 C. and 6 milliliters of water are collected. The calculated amount of water for imidazoline formation is 5.4 milliliters. The resulting product as an 88 percent Xylene solution is a dark brown thick liquid.
- Example 29bA This experiment is performed in the same equipment and in the same manner as employed in Example 28bA.
- a xylene solution of the product of Example 291) containing 40.9 grams (0.025 mole) of the reaction product of 2,6-dimethylol-4-tertiarybutyl phenol and Polyamine N-400 and about 47 grams of xylene.
- To this solution is added With stirring 7.2 grams (0.05 mole) of octanoic acid.
- the reaction mixture is heated at reflux for 3.75 hours at a maximum temperature of 154 C. and 1.3 milliliters of water is collected.
- Oxyalkylation is well known. For purpose of brevity reference is made to Parts 1 and 2 of US. Patent 'No. 2,792,371, dated May 14, 1957, to Dickson in which par- 25 ticular attention is directed to the various patents which describe typical oxyalkylation procedure. Furthermore, manufacturers of alkylene oxides furnish extensive in formation as to the use of oxides. For example, see the technical bulletin entitled Ethylene Oxide which has been distributed by the Jefferson Chemical Company, Houston, Texas. Note also the extensive bibliography in this bulletin and the large number of patents which deal with oxyalkylation processes.
- Example 111/10 The reaction vessel employed is a 4 liter stainless steel autoclave equipped with the usual devices for heating and heat control, a stirrer, inlet and outlet means, etc., which are conventional in this type of apparatus.
- the stirrer is operated at a speed of 250 rpm.
- Into the autoclave is charged 1230 grams (1 mole) of MA, and 500 grams of xylene.
- the autoclave is sealed, swept with nitrogen, stirring started immediately, and heat applied.
- the temperature is allowed to rise to approximately 100 C. at which time the addition to ethylene oxide is started.
- Ethylene oxide is added continuously at such speed that it is absorbed by the reaction mixture as added.
- 132 grams (3 moles) of ethylene oxide is added over 2% hours at a temperature of 100 C. to 120 C. and a maximum pressure of 30 p.s.i.
- Example 10/10 The reaction vessel employed is the same as that used in Example laAO. Into the autoclave is charged 1230 g. (1 mole) of laA and 500 grams of xylene. The autoclave is sealed, swept with nitrogen, stirring is started immediately, and heat is applied. The temperature is allowed to rise to approximately 100 C. at which time the addition of propylene oxide is started. Propylene oxide is added continuously at such speed that it is absorbed by the reaction mixture as added. During the addition 174 g. (3 moles) of propylene oxide are added over 2 hours at a temperature'of 100 to 120 C. and a maximum pressure of 30 lbs. p.s.i.
- Example 152/10 The reaction mass of Example 1aAO is transferred to a larger autoclave (capacity liters). The procedure is repeated so as to add another 174 g. (3 moles) of propylene oxide under substantially the same operating conditions but requiring about 3 hours for the addition.
- Example IaAO At the end of the second step (Example 1aAO the autoclave is opened, g. of sodium methylate is added,
- Example IaOA One mole (919 grams) of MO mixed with 846 grams (three moles) of oleic acid and 300 ml. xylene. The reaction mixture is heated to about 150160 C. over a period of 2 hours until 54 grams (3 moles) of Water are removed. Xylene is then removed under vacuum. The product laOA is xylene soluble.
- This phase of our invention relates to the use of oxyalkylated and other products of the present invention in preventing, breaking or resolving emulsions or" the waterin-oil type, and particularly petroleum emulsions.
- Their use provides an economical and rapid process for resolving petroleum emulsions of the water-in-oil type that are commonly referred to as cut oil, roily oil, emulsified oil, etc., and which comprise fine droplets of naturallyoccurring waters or brines dispersed in a more or less permanent state throughout the oil which constitutes the continuous phase of the emulsion.
- Demulsification includes the preventive step of commingling the demulsifier with the aqueous component which would or might subsequently become either phase of the emulsion in the absence of such precautionary measure.
- demulsifier may be mixed with the hydrocarbon component.
- demulsifying agents employed in the treatment of oil field emulsions are used as such, or after dilution with any suitable solvent, such as Water, petroleum hydrocarbons, such as benzene, toluene, xylene, tar acid oil, cresol, anthracene oil, etc.
- Alcohols particularly aliphatic alcohols, such as methyl alcohol, ethyl alcohol, denatured a1- cohol, propyl alcohol, butyl alcohol, hexyl alcohol, octyl alcohol, etc., are often employed as diluents.
- Miscellaneous solvents such as pine oil, carbon tetrachloride, sulfur dioxide extract obtained in the refining of petroleum, etc.
- the material or materials employed as the demulsifying agent of our process are often admixed with one or more of the solvents customarily used in connection with conventional demulsifying agents.
- said material or materials are often used alone or in admixture with other suitable well-known classes of demulsifying agents.
- demulsifying agents are useful in a water-soluble form, or in an oil-soluble form, or in a form exhibiting both oil and water-solubility. Sometimes they are used in a form which exhibits relatively limited oil-solubility. However, since such reagents are frequently used in a ratio of 1 to 10,000, or 1 to 20,000, or 1 to 30,000, or even 1 to 40,000, or 1 to 50,000, as in desalting practice,
- One type of procedure is to accumulate a volume of emulsified oil in a tank and conduct a batch treatment type of demulsification procedure to recover clean oil.
- the emulsion is admixed with the demulsifier, for example by agitating the tank of emulsion and slowly dripping demulsifier into the emulsion. In some cases mixing is achieved by heating the emulsion while dripping in the demulsifier, depending upon the convection currents in the emulsion to produce satisfactory admixture.
- a circulating pump withdraws emulsion from, e.g. the bottom of the tank, and re-introduces it into the top of the tank, the demulsifier being added, for example, at the suction side of said circulating pump.
- the demulsifier is introduced into the well fluids at the well-head or at some point between the well-head and the final oil storage tank, by means of an adjustable proportioning mechanism or proportioning pump.
- an adjustable proportioning mechanism or proportioning pump Ordinarily the flow of fluids through the subsequent lines and fittings suffices to produce the desired degree of mixture of demulsifier and emulsion, although in some instances additional mixing devices may be introduced into the flow system.
- the system may include various mechanical devices for withdrawing free water, separating entrained water, or accomplishing quiescent settling of the chemicalized emulsion. Heating devices may likewise be incorporated in any of the treating procedures described herein.
- a third type of application (down-the-hole) of demulsifier to emulsion is to introduce the demulsifier either periodically or continuously in diluted or undiluted form into the well and to allow it to come ot the surface with the well fluids, and then to flow the chemicalized emulsion through any desirable surface equipment, such as employed in the other treating procedures.
- This particular type of application is decidedly useful when the demulsifier is used in connection with acidification of calcareous oil-bearing strata, especially if suspended in or dissolved in the acid employed for acidification.
- a reservoir to hold the demulsifier of the kind described (diluted or undiluted) is placed at the well-head where the effluent liquids leave the well.
- This reservoir or container which may vary from 5 gallons to 50 gallons for convenience, is connected to a proportioning pump which injects the demulsifier drop-wise into the fluids leaving the well.
- Such chemicalized fluids pass through the flowline into a settling tank.
- the oxyalkylated products herein specified as demulsifiers can be conveniently used without dilution. However, as previously noted, they may be diluted as desired with any suitable solvent. Selection of the solvent will vary, depending upon the solubility characteristics of the oxyalkylated product, and, of course will be dictated in part by economic consideration, i.e., cost. The products herein described are useful not only in diluted form but also admixedwith other chemical demulsifiers.
- the compounds are also useful in preventing the formation of emulsions during transit.
- the emulsion generally a Water-in-oil type, so produced is characterized by the fact that the dispersed phase is sea water.
- Typical examples are shipments of oil from the Near East to Japan, Australia, etc., and various quantities shipped to the west coast of the USA. and, for that matter, to the east coast of the USA.
- Oil in transit can be effectively inhibited against emulsification by adding a small amount, i.e., sufiicient substantially to reduce the tendency of the fuel to emulsify, of the demulsifiers described above.
- such concentrates may comprise a petroleum distillate or other suitable liquid hydrocarbon in admixture with a demulsifier as embodied herein and wherein the demulsifier is present in an amount of about 10 to 75% or higher but preferably 10 to 25% based on the weight of the concentrate.
- such concentrates may comprise a suitable hydrocarbon vehicle, e.g., diesel fuels, kerosenes, and other mineral oil fractions, in which there is dissolved or dispersed a demulsifier in amounts varying from about 10 35 to 75% by weight of the concentrate, and, in still more, specific illustration, a suitable concentrate comprising about 50% by Weight of demulsifier in admixture with a petroleum hydrocarbon of diesel fuel grade.
- Emulsions'of the oil-in-water class comprise organic oily materials, which, although immiscible with water or aqueous or non-oily media, are distributed or discompound of our invention at the refinery or at the loadpersed as small drops throughout a continuous body of ing dock using a proportional pump.
- the pumping dcnon-oily medium.
- the proportion of dispersed oily mavice adds the product so that it is entirely mixed and thus terial is in many and possibly most cases a minor one.
- test compositions are prepared by disduced in the catalytic dehydrogenation of butylene to solving 0.2% of the following compounds of this invenproduce b-utadiene; styrene-in-water emulsions in syntion in a diesel fuel, mixing the thus prepared solution thetic rubber plants; synthetic latex-in-water emulsions, with an equal amount of either distilled water or synfound in plants producing copolymer butadiene-styrene thetic sea water, and subjecting the resulting admixtures or GRS synthetic rubber; oil-in-water emulsions occurto stirring at the rate of 1500 revolutions per minute.
- Test compositions containing the compounds shown in the following table either do not emulsify or the emulsions are completely resolved within a short time after stirring is stopped.
- Essential oils comprise non-saponifiable materials like terpenes, lactones, and alcohols. They also contain saponifiable esters or mixtures of saponificable and nonsaponifiable materials. Steam distillation and other production procedures sometimes cause oil-in-water emulsions to be produced, from which the valuable essential oils are difficultly recoverable.
- the foregoing examples illustrate the fact that, within the broad genus of oil-in-water emulsions, there are at least three important sub-genera.
- the dispersed oily material is respectively non-saponifiable, saponifiable, and a mixture of non-saponifiable and saponifiable materials.
- the most important emulsions of non saponifiable material in water are petroleum oil-in-water emulsions.
- Saponifiable oil-in-Water emulsions have dispersed phases comprising, for example, saponifiahle oils and fats and fatty acids, saponifiable oily or fatty esters, and the organic components of such esters to the extent such components are immiscible with aqueous media.
- Emulsions produced from certain blended lubricating compositions containing both mineral and fatty oil ingredients are examples of the third sub-genus.
- Oil-in-water emulsions contain widely different proportions of dispersed phase. Where the emulsion is a waste product resulting from water flushing of manufacturing areas or equipment, the oil content may be only a few parts per million. Resin emulsion paints, as produced, contain a major proportion of dispersed phase. Naturallyoccurring oil-field emulsions of the oil-in-water class carry crude oil in proportions varying from a few parts per million to about or higher in certain cases.
- This phase of the present invention is concerned with the resolution of those emulsions of the oil-in-water class which contain a minor proportion of dispersed phase, ranging, for example, from 20% or higher down to 50 parts per million or less.
- emulsion stability In emulsions having high proportions of dispersed phase, appreciable amount of some emulsifying agent are probably present, to account for their stability. In the case of more dilute emulsions, containing 1% or less of dispersed phase, there may be difficulty in accounting for their stability on the basis of the presence of an emulsifying agent in the conventional sense. For example, steam condensate frequently contains very small proportions of refined petroleum lubricating oil in extremely stable dispersion; yet neither the steam condensate nor the refined hydrocarbon oil would appear to contain anything suitable to stabilize the emulsion. In such cases, emulsion stability must probably be predictated on some basis other than the presence of an emulsifying agent.
- emulsions are by-products of manufacturing procedures in which the composition of the emulsion is known.
- the emulsions to be resolved are either naturally-occurring or are acci dentally or unintentionally produced; or in any event they do not result from a deliberate or premeditated procedure.
- the emulsifying agent is unknown and as a matter of fact an emulsifying agent, in the conventional sense, may be felt to be absent. It is obviously very difiicult or even impossible to recommend a resolution procedure for the treatment of such latter emulsions, on the basis of theoretical knowledge.
- the process which constitutes this phase of the present invention consists in subjecting an emulsion of the oil-inwater class to the action of a demulsifier of the kind de' scribed, thereby causing the oil particles in the emulsion to coalesce sufficiently to rise to the surface of the nonoily layer (or settle to the bottom, if the oil density is greater) when the mixture is allowed to stand in the quiescent state after treatment with the reagent or demulsifier.
- Applicability of the present process can be readily de termined by direct trial on any emulsion, without reference to theoretical considerations. This fact facilitates its application to naturally-occurring emulsions, and to emulsions accidentally, unintentionally, or unavoidably produced; since no laboratory experimentation, to discover the nature of the emulsion components or of the emulsifying agent, is required.
- our reagents are useful in undiluted form or diluted with any suitable solvent.
- Water is commonly found to be a highly satisfactory solvent, because of its ready availability and negligible cost; but in some cases, nonaqueous solvents such as an aromatic petroleum solvent may be found preferable.
- the products themselves may exhibit solubilities ranging from rather modest waterdispersibility to full and complete dispersibility in that solvent. Because of the small proportions in which our reagents are customarily employed in practicing our process, apparent solubility in bulk has little significance. In the extremely low concentrations of use they undoubtedly exhibit appreciable water-solubility or water-clispersibility as well as oil-solubility or oil-dispersibility.
- Our reagents may be employed alone, or they may in some instances be employed to advantage admixed with other and compatible oil-in-water demulsifiers.
- agitation and mixing are achieved by stirring together or shaking together the emulsion and reagent.
- distinctly improved results are obtained by the use of air or other gaseous medium.
- the volume of gas employed is relatively small and the conditions of its introduction relatively mild, it behaves as a means of securing ordinary agitation.
- aeration is effected by introducing a gas directly under pressure or from porous plates or by means of aeration cells, the effect is often importantly improved.
- a sub-aeration type flotation cell of the kind commonly employed in ore beneficiation operations, is an extremely useful adjunct in the application of our reagents to many emulsions. It frequently accelerates the separation of the emulsion, reduces reagent requirements, or produces an improved effluent. Sometimes all three improvements are observable.
- Heat is ordinarily of little importance in resolving oilin-water class emulsions with our reagents although there are some instances Where heat is a useful adjunct. This is especially true where the viscosity of the continuous phase of the emulsion is appreciably higher than that of water.
- the reagent feed rate also has an optimum range, which is sufficiently wide, however, to meet the tolerances required for the variances encountered daily in commercial operations. A large excess of reagent can produce distinctly unfavorable results.
- Example An oil-in-water class emulsion produced from an oil Well in the Coalinga field located in Southern California contains about 1,500 ppm. of crude oil, on the average, and is stable for days in the absence of external resolution.
- Our process is practiced by flowing the well fluids, comprising free crude oil, oil-in-water emulsion and natural gas, through a gas separator, then to a steel tank of 5,000 barrel capacity. In this tank the oil-in-water emulsionfalls to the bottom and is separated from the free oil.
- the oil-in-water emulsion is withdrawn from the bottom of the tank and the reagent of Example 2-1 introduced into the stream. The proportion employed is about 5 ppm. based on the volume of emulsion, on the average.
- the chemicalized emulsion flows to a second tank, mixing being achieved in the pipe. In the second tank it is allowed to stand quiescent. Clear water is withdrawn from the bottom of this tank, separated oil from the top.
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Description
No Drawing.
20 Qiairns.
This application is a continuation-in-part of our copending application Serial No. 730,510, filed April 24, 1958, now abandoned. This invention relates to the prevention and/ or resolution of emulsions employing as treat ng agents compounds which are (l) oxyalkylated, (2) acyiated, (3) oxyalirylated then acylated, (4) acylated then oxyalkylated, and acylated, then oxyalkylated and then acylated, monomeric polyaminomethyl phenols. These substituted phenols are produced by a process which is characterized by reacting a preformed methylol phenol (i.e. formed prior to the addition of the polyamine) with at least one mole of a secondary polyamine per equivalent of methylol group on the phenol, in the absence of an extraneous catalyst (in the case of an aqueous reaction mixture, the pH of the reaction mixture being determined solely by the methylol phenol and the secondary poly amine), until about one mole of water per equivalent of methylol group is removed; and then reacting this product with (1) an oxyalkylating agent, (2) an acylating agent, (3) an oxyalkylating agent then an acylating agent, (4) an acylating agent then an oxalkylating agent or (5) an acylating agent then an oxyalkylating agent and then an acylating agent.
to reasons for the unexpected monomeric form and properties of the polyaminomethyl phenol are not understood. However, we have discovered that when (l) a preformed methylolphenol (i.e. formed prior to the addition of the polyamine) employed as a starting material is reacted with (2) a polyamine which contains at least one secondary amino group (3) in amounts of at least one mole of secondary polyamine per equivalent of methylol group on the phenol, (4) in the absence of an extraneous catalyst, until (5) about one mole of water per equivalent of methylol group is removed, then a monomeric polyaminomethyl phenol is produced which is capable of being oxyalkylated, acylated, oxyalkylated then acylated, or acylated then oxyalkylated, or acylated, then oxyalkylated and then acylated to provide the superior products empioyed in the process of this invention. All of the above five conditions are critical for the production of these monomeric polyaminomethyl phenols.
In contrast, if the methylol phenol is not preformed but is formed in the presence of the polyamine, or the preformed methylol phenol is condensed with the polyamine in the presence of an extraneous catalyst, either acidic or basic, for example, basic or alkaline materials such as NaOH, Ca(OH) Na CO sodium methylate, etc., a polymeric product is formed. Thus, if an alkali metal phenate is employed in place of the free phenol, or even if a lesser quantity of alkali metal is present than is required to form the phenate, a polymeric product is formed. Where a polyamine containing only primary amino groups and no secondary amino groups is reacted with a methylol phenol, a polymeric product is also produced. Similarly, where less than one mole of secondary amine is reacted per equivalent of methylol group, a polymeric product is also formed.
In general, the monomeric polyaminomethyl phenols are prepared by condensing the methylol phenol with the secondary amine as disclosed above, said condensation being conducted at a temperature sufiiciently high to eliminate water but below the pyrolytic point of the reactants and product, for example, at 80 to 200 C., but
Patented Sept. 8, 1964 preferably at to C. During the course of the condensation Water can be removed by any suitable means, for example, by use of an azeotroping agent, reduced pressure, combinations thereof, etc. Measuring the water given olf during the reaction is a convenient method of judging completion of the reaction.
The classes of methylol phenols employed in the condensation are as follows:
Monophenols.-A phenol containing 1, 2 or 3 methylol groups in the ortho or para position (i.e. the 2, 4, 6 positions), the remaining positions on the ring containing hydrogen or groups which do not interfere with the polyamine-methylol group condensation, for example, alkyl, alkenyl, cycloalkyl, phenyl, halogen, and alkoxy, etc., groups, and having but one nuclear linked hydroxyl group.
Diphen0ls.-One type is a diphenol containing two hydroxybenzene radicals directly joined together through the ortho or para (i.e. 2, 4 or 6) position with a bond joining the carbon of one ring with the carbon of the other ring, each hydroxybenzene radical containing 1 to 2 methylol groups in the 2, 4 or 6 positions, the remaining positions on each ring containing hydrogen or groups which do not interfere with the polyamine-methylol group condensation, for example, alkyl, alkenyl, cycloalkyl, phenyl, halogen, alkoxy, etc., groups, and having but two nuclear linked hydroxyl groups.
A second type is a diphenol containing two hydroxybenzene radicals joined together through the ortho or para (i.e. 2, 4 or 6 position with a bridge joining the carbon of one ring to a carbon of the other ring, said bridge being, for example, alkylene, alkylidene, oxygen, carbonyl, sulfur, sulfoxide and sulfone, etc., each hydroxybenzene radical containing 1 to 2 methylol groups in the 2, 4 or 6 positions, the remaining positions on each ring containing hydrogen or groups which do not interfere with the polyaminomethylol group condensation, for example, alkyl, alkenyl, cycloalkyl, phenyl, halogen, alkoxy, etc., groups, and having but two nuclear linked hydroxyl groups.
The secondary polyamines employed in producing the condensate are illustrated by the following general formula:
where at least one of the Rs contains an amino group and the Rs contain alkyl, alkoxy, cycloalkyl, aryl, aralkyl, alkaryl, radicals and the corresponding radicals containing heterocyclic radicals, hydroxy radicals, etc. The Rs may also be joined together to form heterocyclic polyarnines. The preferred classes of polyamines are the alkylene polyamines, the hydroxylated alkylene polyamines, branched polyamines containing at least three primary amino groups, and polyamines containing cyclic amidine groups. The only limitation is that there shall be present in the polyamine at least one secondary amino group which is not bonded directly to a negative radical which reduces the basicity of the amine, such as a phenyl group.
An unusual feature of the products employed in the process of the present invention is the discovery that methylol phenols react more readily under the herein specified conditions with secondary amino groups than with primary amino groups. Thus, where both primary and secondary amino groups are present in the same molecule, reaction occurs more readily with the secondary amino group. However, where the polyarnine contains only primary amino groups, the product formed under reaction conditions as mentioned above is an insoluble resin. In contrast, where the same number of primary amino groups are present on the amine in addition to at least one secondary amino group, reaction occurs predominantly with the secondary amino group to form nonresinous derivatives. Thus, where trimethylol phenol is reacted with ethylene diamine, an insoluble resinous composition is produced. However, where diethylene triamine, a compound having just as many primary amino groups as ethylene diamine, is reacted, according to this invention a non-resinous product is unexpectedly formed.
The term monomeric as employed in the specification and claims refers to a polyaminomethylphenol containing Within the molecular unit one aromatic unit corresponding to the aromatic unit derived from the starting methylol phenol and one polyamine unit for each methylol group originally in the phenol. This is in contrast to a polymeric or resinous polyaminomethyl phenol containing within the molecular unit more than one aromatic unit and/ or more than one polyamino unit for each methylol group.
The monomeric products produced by the condensation of the methylol phenol and the secondary amine may be illustrated by the following idealized formula:
where A is the aromatic unit corresponding to that of the methylol reactant, and the remainder of the molecule is the polyaminomet'nyl radical, one for each of the original methylol groups.
This condensation reaction may be followed by oxyalkylaltion in the conventional manner, for example, by means of an alpha-beta alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide, octylene oxide, a higher alkylene oxide, styrene oxide, glycide, methylglycide, etc., or combinations thereof. Depending on the particular application desired, one may combine a large proportion of alkylene oxide, particularly ethylene oxide, propylene oxide, a combination or alternate additions or propylene oxide and ethylene oxide, or smaller proportions thereof in relation to the methylol phenolamine condensation product. Thus, the molar ratio of alkylene oxide to amine condensate can range within wide limits, for example, from a 1:1 mole ratio to a ratio of 1000zl, or higher, but preferably 1 to 200. For example, in demulsification extremely high alkylene oxide ratios are advantageously employed such as 200-300 or more pounds of alkylene oxide per pound of amine condensate. By proper control, desired hydrophilic or hydrophobic properties are imparted to the composition. As is well known, oxyalkylation reactions are conducted under a wide variety of conditions, at low or high pressures, at low or high temperatures, in the presence or absence of catalyst, solvent, etc. For instance oxyalkylation reactions can be carried out at temperatures of from 80-200 C., and pressures of from to 200 p.s.i., and times of from min. to several days. Preferably oxyalkylation reactions are carried out at 80 to 120 C. and 10 to 30 psi. For conditions of oxyalkylation reactions see U.S. Patent 2,792,369 and other patents mentioned therein.
As in the amine condensation, acylation is conducted at a temperature suificiently high to eliminate water and below the pyrolytic point of the reactants and the reaction products. In general, the reaction is carried out at a temperature of from 140 to 280 C., but preferably at 140 to 200 C. In acylating, one should control the reaction so that the phenolic hydroxyls are not acylated. Because acyl halides and anhydrides are capable of reacting with phenolic hydroxyls, this type of acylation should be avoided. It should be realized that either oxyalkylation or acylation can be employed alone or each alternately, either one preceding the other. In addition, the amine condensate can be acylated, then oxyalkylated and then reacylated. The amount of acylation agent reacted will depend on reactive groups or the compounds and properties desired in the final product, for example,
the molar ratios of acylation agent to amine condensate can range from 1 to 15, or higher, but preferabley 1 to 4.
Where the above amine condensates are treated With alkylene oxides, the product formed will depend on many factors, for example, whether the amine employed is hydroxylated, etc. Where the amines employed are nonhydroxylated, the amine condensate is at least susceptible to oxyalkylation through the phenolic hydroxyl radical. Although the polyamine is non-hydroxylated, it may have one or more primary or secondary amino groups which may be oxyalkylated, for example, in the case of tetraethylene pentamine. Such groups may or may not be I susceptible to oxyalkylation for reasons which are obsome. Where the non-hydroxylated amine contains a plurality of secondary amino groups, wherein one or more is susceptible to oxyalkylation, or primary amino groups, oxyalkylation may occur in those positions. Thus, in the case of the non-hydroxylated polyamines oxyalkylation may take place not only at the phenolic hydroxyl group but also at one or more of the available amino groups. Where the amine condensate is hydroxyalkylated, this latter group furnishes an additional position of oxyalkylation susceptibility.
The product formed in acylation will vary with the particular polyaminomethyl phenol employed. It may be an ester or an amide depending on the available reactive groups. If, however, after forming the amide at a temperature between 250 C., but usually not above 200 C., one heats such products at a higher range, approximately 250-280 C., or higher, possibly up to 300 C. for a suitable period of time, for example, 1-2 hours or longer, one can in many cases recover a second mole of water for each mole of carboxylic acid employed, the first mole of water being evolved during amidification. The product formed in such cases is believed to contain a cyclic amidine ring such as an imidazoline or a tetrahydropyrimidine ring.
Ordinarily the methods employed for the production of amino imidazolines result in the formation of substantial amounts of other products such as amido imidazolines. However, certain procedures are well known by which the yield of amino imidazolines is comparatively high as, for example, by the use of a polyamine in which one of the terminal hydrogen atoms has been replaced by a low molal alkyl group or an hydroxyalkyl group, and by the use of salts in which the polyamine has been converted into a monosalt such as combination with hydrochloric acid or'paratoluene sulfonic acid. Other procedures involve reaction with a hydroxyalkyl ethylene diamine and further treatment of such imidazoline having a hydroxyalkyl substituent with two or more moles of ethylene imine. Other well known procedures may be employed to give comparatively high yields.
Other very useful derivatives comprise acid salts and quaternary salts, derived therefrom. Since the compositions contain basic nitrogen groups, they are capable of reacting with inorganic acids, for example hydrohalogens (HCl, HBr, HI), sulfuric acid, phosphoric acid, etc., aliphatic acids (acetic, propionic, glycolic, diglycolic, etc.), aromatic acids (benzoic, salicylic, phthalic, etc.), and organic compounds capable of forming salts, for example, those having the general formula RX wherein R is an organic group, such as an alkyl group (e.g. methyl, ethyl, propyl, butyl, octyl, nonyl, decyl, undecy-l, dodecyl, tridecyl, pentadecyl, oleyl, octadecyl, etc.), cycloalkyl (e.g. cyclopentyl, cyclohexyl, etc.), aralkyl (e.g. benzyl, etc.), and the like, and X is a radical capable of forming a salt such as those derived from acids (e.g. halide, sulfate, phosphate, sulfonates, etc., radicals). The preparation of these salts and quaternary compounds is well known to the chemical art. For example, they may be prepared by adding suitable acids (for example, any of those mentioned herein as acylating agents) to solutions of the basic composition or by heating such compounds as alkyl halides with these compositions. Diacid and quaternary salts can also be formed by reacting alkylene dihalides, polyacids, etc. The number of moles of acid and quaternary compounds that may react with the composition of this invention will, of course, depend on the number of basic nitrogen groups in the molecule. These salts may be represented by the general formula N+ X-, wherein N comprises the part of the compound containing the nitrogen group which has been rendered positively charged by the H or R of the alkylating compound and X represents the anion derived from the alkylating compound.
THE METHYLOL PHENOL As previously stated, the methylol phenols include monophenols and diphenols. The methylol groups on the phenol are either in one or two ortho positions or in the para position of the phenolic rings. The remaining phenolic ring positions are either unsubstituted or substituted with groups not interfering with the amine methylol condensation. Thus, the monopghenols have 1, 2 or 3 methylol groups and the diphenols contain 1, 2, 3 or 4 methylol groups.
The following is the monophenol most advantageously employed:
HOCHr- CH2OH HO CH1 CH2OH where R is an aliphatic saturated or unsaturated hydrocarbon having, for example, 1-30 carbon atoms, for example, methyl, ethyl, propyl, butyl, sec-butyl, tertbutyl, amyl, tert-amyl, hexyl, tert-hexyl, octyl, nonyl, decyl, dodecyl, octo-decyl, etc., the corresponding unsaturated groups, etc.
The third monophenol advantageously employed is:
HO CH2 CHzOH l CHzOH where R comprises an aliphatic saturated or unsaturated hydrocarbon as stated above in the second monophenol, for example, that derived from cardanol or hydrocardan01.
The following employed:
One species is are diphenol species advantageously GH2OH CH OH If I CHzOH CHzOH where R is hydrogen or a lower alkyl, preferably methyl.
A second species is where R has the same meaning as that of the second species of the monophenols and R is hydrogen or a lower alkyl, preferably methyl.
We can employ a wide variety of methylol phenols in the reaction, and the reaction appears to be generally applicable to the classes of phenols heretofore specified. Examples of suitable methylol phenols include:
Monophenols:
Z-methylol phenol 2,6-dimethylol, 4-methyl phenol 2,4,6-trimethylol phenol 2,6-dimethylol, 4-cyclohexyl phenol 2,6-dimethylol-4-phenyl phenol 2,6-dimethylol-4-methoxyphenol 2,6-dimethylol-4-chlorophenol 2,6-dimethylol-3-methylphenol 2,6-dimethylol-4rsec-butylphenol 2,6-dimethylol, 3,5-dimethy1-4-chlorophenol 2,4,6-trimethylol, 3-pentadecyl phenol 2,4,6-trimethylol, 3-pentadecadienyl phenol.
Diphenols:
onion onion CH2OH CHzOH CH2OH 0112011 onion onion CH3 (3H3 0112013 onion 2212011 on. 2113 2112011 HO -0H, -on
i onion 0112011 OH OH HOCH2OCH:OCHOH l CHzOH CHzOH OH on uoom-Q-om0omon C12H25 Ciz zs OH OH I (FHI! HOCH2 J OH1OH CH3 l OH2OH CH2OH OH OH a HOCH2 CHZOH CH l CH CH3 CHzOH CHzOH CH3 l CH2OH CHZOH (IJH2OH ([JH2OH l omorr onion CHzOH CHZOH CH2OH CHzOH (DH (|)H no omO-s..-omon C12H25 012 2 CHzOH CHzOH I I? I CHzOH CH2OH CHzOH CHZOH l I? l I 0 l CH OH CHzOH CHzOH (l HzOH CHzOH lHzoH Examples of additional methylol phenols which can be employed to give the useful products of this invention are described in The Chemistry of Phenolic Resins, by Robert W. Martin, Tables V and VI, pp. 32-39 (Wiley, 1956).
THE POLYAMINE As noted previously, the general formula for the polyamine 1s R HN/ This indicates that a wide variety of reactive secondary polyamines can be employed, including aliphatic polyamines, cycloaliphatic polyamines, aromatic polyamines (provided the aromatic polyamine has at least one secondary amine which has no negative group, such as a phenyl group directly bonded thereto) heterocyclic polyamines and polyamines containing mixtures of the above groups. Thus, the term polyamine includes compounds having one amino group on one kind of radical, for example, an aliphatic radical, and another amino group on the heterocyclic radical as in the case of the following formula:
provided, of course, the polyamine has at least one secondary amino group capable of condensing with the methylol group. It also includes compounds which are totally heterocyclic, having a similarly reactive secondary amino group. It also includes polyamines having other elements besides carbon, hydrogen and nitrogen, for example, those also containing oxygen, sulfur, etc. As previously stated, the preferred embodiments of the present invention are the alkylene polyamines, the hydroxylated alkylene polyamines and the amino cyclic amidines.
Polyamines are available commercially and can be prepared by well-known methods. It is well known that olefin dichlorides, particularly those containing from 2 to 10 carbon atoms, can be reacted with ammonia or amines to give alkylene polyarnines. If, instead of using ethylene dichloride, the corresponding propylene, butylene, amylene or higher molecular weight dichlorides are used, one then obtains the comparable homologues. One can also alpha-omega dialkyl ethers such as CICH OCH CI; ClCH CH OCH CH Cl, and the like. Such polyamines can be alkylated in the manner commonly employed for alkylating monoarnines. Such alkylation results in products which are symmetrically or non-symmetrically alkylated. The symmetrically alkylated polyamines are most readily obtainable. For instance, :alkylated products can be derived by reaction between alkyl chlorides, such as propyl chloride, butyl chloride, amyl chloride, cetyl chloride, and the like and a polyamine having one or more primary amino groups. Such reactions result in the formation of hydrochloric acid, and hence the resultant prod not is an amine hydrochloride. The conventional method for conversion into the base is to treat with dilute caustic solution. Alkylation is not limited to the introduction of an alkyl group, but as a matter of fact, the radical introduced can be characterized by a carbon atom chain interrupted at least once by an oxygen atom. In other words, alkylation is accomplished by compounds which are essentially alkyoxyalkyl chlorides, as, for example, the following:
The reaction involving the alkylene dichlorides is not limited to ammonia, but also involves amines, such as ethylamine, propylamine, butylamine, octylamine, decylamine, cetylamine, dodecylamine, etc. Cyclo-aliphatic and aromatic amines are also reactive. Similarly, the reaction also involves the comparable secondary amines, in which various alkyl radicals previously mentioned appear twice and are types in which two dissimilar radicals appear, for instance, amyl butylamine, hexyl octyl-amine, etc. Furthermore, compounds derived by reactions involving alkylene dichlorides and a mixture of ammonia and amines, or a mixture of two difierent amines are useful. However, one need not employ a polyamine having an alkyl radical. For instance, any suitable polyalkylene polyamine, such as an ethylene polyamine, a propylene polyamine, etc., treated with ethylene oxide or similar oxyalkylating agent are useful. Furthermore, various hydroxylated amines, such as monoethanolamine, monopropanolamine, and the like, are also treated with a suitable alkylene dichloride, such as ethylene dichloride, propylene dichloride, etc.
As to the introduction of a hydroxylated group, one can use any one of a number of well-known procedures such as alkylation, involving a chlorhydrin, such as ethylene chlorhydrin, glycerol chlorhydrin, or the like.
Such reactions are entirely comparable to the alkylation reaction involving alkyl chlorides previously described. Other reactions involve the use of an alkylene oxide, such as ethylene oxide, propylene oxide, butylene oxide, octylene oxide, styrene oxide or the like. Glycide is advantageously employed. The type of reaction just referred to is well known and results in the introduction of a hydroxylated or polyhydroxylated' radical in an amino hydrogen position. It is also possible to introduce a hydroxylated oxyhydrocarbon atom; for instance, instead of using the chlorhydn'n corresponding to ethylene glycol, one employs the chlorhydrin corresponding to diethylene glycol. Similarly, instead of using the chlorhydrin corresponding to glycerol, one employs the chlorhydrin corresponding to diglycerol.
From the above description it can be seen that many of the above polyamines can be characterized by the general formula R x R where the Rs, which are the same or different, comprise hydrogen, alkyl, cycloalkyl, aryl, alkyloxyalkyl, hydroxylated alkyl, hydroxylated alkyloxyalkyl, etc, radicals, x is zero or a whole number of at least one, for example 1 to 10, but preferably 1 to 3, provided the polyamine contains at least one secondary amino group, and n is a whole number, 2 or greater, for example 210, but preferably 2-5. Of course, it should be realized that the amino or hydroxyl group may be modified by acylation to form amides, esters or mixtures thereof, prior to the methylolamino condensation provided at least one active secondary amine group remains on the molecule. Any of the suitable acylating agents herein described may be employed in this acylation. Prior acylation of the amine can advantageously be used instead of acylation subsequent to amine condensation.
A particularly useful class of polyamines is a class of branched polyamines. These branched polyamines are polyalkylene polyamines wherein the branched group is a side chain containing on the average at least one nitrogenbonded aminoalkylene anna s group per nine amino units present on the main chain, for example 14 of such branched chains per nine units on the main chain, but preferably one side chain unit per nine main chain units. Thus, these polyamines contain at least three primary amino groups and at least one tertiary amino group in addition to at least one secondary amino group.
These branched polyamines may be expressed by the wherein R is an alkylene group such as ethylene, propylene, butylene. and other homologues (both straight chained and branched), etc., but preferably ethylene; and x, y and z are integers, x being for'exarnple, from 4 to 24 or more but preferably 6 to 18, y being for example 1 to 6 or more but preferably 1 to 3, and z being for example 0-6 but preferably 0-1. The x and y units may be sequential, alternative, orderly or randomly distributed.
The preferred class of branched polyamines includes those of the formula formula l I l R I IH 11 where n is an integer, for example 1-20 or more but preferably 1-3, wherein R is preferably ethylene, but may be propylene, butylene, etc. (straight chained or branched).
The particularly preferred branched polyamines are presented by the following formula:
The radicals in the brackets may be joined in a headto-head or a head-to-tail fashion. Compounds described by this formula wherein n: 1-3 are manufactured and sold by Dow Chemical Company as Polyamines N400, N-800, N-1200, etc. Polyamine N-400 has the above formula wherein n=1 and Was the branched polyamine employed in all of the specific examples.
The branched polyamines can be prepared by a wide variety of methods. One method comprises the reaction of ethanolamine and ammonia under pressure over a fixed bed of a metal hydrogenation catalyst. By controlling the conditions of this reaction one can obtain various amounts of piperazine and polyamines as well as the branched chain polyalkylene polyamine. This process is described in Australian Patent No. 42,189 and in the East German Patent 14,480 (March 17, 1958) reported in Chem. Abstracts, August 10, 1958, 14129.
The branched polyamines can also be prepared by the following reactions:
l CH2 Variations on the above procedure can produce other branched polyamines.
The branched nature of the polyamine imparts unusual properties to the polyamine and its derivatives. Cyclic aliphatic polyamines having at least one secondary amino group such as piperazine, etc., can also be employed.
It should be understood that diamines containing a secondary amino group may be employed. Thus, where x in the linear polyalkylene amine is equal to zero, at least one of the Rs would have to be hydrogen, for example, a compound of the following formula:
Cm u
NCH -CH,NH
-I Suitable polyamines also include polyamines wherein the alkylene group or groups are interrupted by an oxygen radical, for example,
R R R R x R or mixtures of these groups and alkylene groups, for example,
R R R where R, n and x has the meaning previously stated for the linear polyamine.
For convenience the aliphatic polyamines have been classified as nonhydroxylated and hydroxylated alkylene polyamino amines. The following are representative members of the nonhydroxylated series:
Diethylene triamine,
Dipropylene triamine,
Dibutylene triamine, etc.
Triethylene tetramine,
Tripropylene tetramine,
Tributylene tetramine, etc.
Tetraethylene pentarnine,
Tetrapropylene pentamine,
Tetrabutylene pentamine, etc.,
Mixtures of the above,
Mixed ethylene, propylene, and/or butylene, etc., polyamines and other members of the series.
The above polyamines modified with higher molecular weight aliphatic groups, for example, those having from 8-3O or more carbon atoms, a typical example of which is H H H NH2C 2H4NC zHr-NC 2H4N- C ia aa where the aliphatic group is derived from any suitable source, for example, from compounds of animal or vegetable origin, such as coconut oil, tallow, tall oil, soya, etc., are very useful. In addition, the polyamine can contain other alkylene groups, fewer amino groups, additional Examples of polyamines having hydroxylated groups include the following:
higher aliphatic groups, etc., provided the polyamine has where R is alkyl and Z is an alkylene group containing phenyl groups on some of the alkylene radicals since the phenyl group is not attached directly to the secondary amino group.
In addition, the alkylene group substituted with a hydroxy group OH H is reactive.
CHs
Z-undecylimidazoline Z-heptadecylimidazoline Z-oIeylimidazoline l-N-decylaminoethyl, Z-ethylimidazoline Z-methyl, l-hexadecylaminoethylaminoethylimidazoline 1-dodecylaminopropylimidazoline lstearoyloxyethyl) aminoethylimidazoline l-ste aramidoet'nylamino ethylimid az oline 2-heptadecyl, 4,5-dimethylimidazoline 1-dodecylaminohexylimidazoline 1-stearoyloxyethylaminohexylimidazoline Z-heptadecyl, l-methylaminoethyl tetrahydropyrimidine 4-methy1, 2-dodecyl, 1-methylaminoethylaminoethyl tetrahydropyrirnidine As previously stated, there must be reacted at least one mole of polyamine per equivalent of methylol group. The upper limit to the amount of amine present will be determined by convenience and economics, for example, 1 or more moles of polyamine per equivalent of methylol group can be employed.
The following examples are illustrative of the preparation of the polyaminomethylol phenol condensate and are not intended for purposes of limitation.
The following general procedure is employed in preparing the polyamine-methylol condensate. The methylolphenol is generally mixed or slowly added to the polyamine in ratios of 1 mole of polyamine per equivalent of methylol group on the phenol. However, where the polyamine is added to the methylolphenol, addition is carried out below 60 C. until at least one mole of polyamine per methylol group has been added. Enough of a suitable azeotroping agent is then added to remove water (benzene, toluene, or xylene) and heat applied. After removal of the calculated amount of water from the reaction mixture (one mole of water per equivalent of methylol group) heating is stopped and the azeotroping agent is evaporated off under vacuum. Although the reaction takes place at room temperature, higher temperatures are required to complete the reaction. Thus, the temperature during the reaction generally varies from 80l60 C. and the time from 424 hours. In general, the reaction can be effected in the lower time range employing higher temperatures. However, the time test of completion of reaction is the amount of water removed.
Example 1a This example illustrates the reaction of a methylolmonophenol and a polyamine. A liter flask is employed with a conventional stirring device, thermometer phase separating trap condenser, heating mantle, etc. 70% aqueous 2,4,6 trimethylol phenol which can be prepared by conventional procedures or purchased in the open market, in this instance, the latter, is employed. The amount used is one gram mole, i.e. 182 grams, of anhydrous trimethylol phenol in 82 grams of water. This represents three equivalents of methylol groups. This solution is added dropwise with stirring to three gram moles (309 grams) of diethylene triamine dissolved in ml. of xylene over about 30 minutes. An exothermic reaction takes place at this point but the temperature is maintained below approximately 60 C. The temperature is then raised so that distillation takes place with the removal of the predetermined amount of water, i.e., the water of solution as well as water of reaction. The water' of reaction represents 3 gram moles or 54 grams.
The entire procedure including the initial addition of the trimethylol phenol until the end of the reaction is approximately 6 hours. At the end of the reaction period the xylene is removed, using a vacuum of approximately 80 mm. The resulting product is a viscous water-soluble liquid of a dark red color.
Example 28a This example illustrates. the reaction of a methylolmonophenol and a branched polyamine. A one liter flask is employed equipped with a conventional stirring device, thermometer, phase separating trap, condenser, heating mantle, etc. Polyamine N-400, 200 grams (0.50 mole), is placed in the flask and mixed with 150 grams of xylene. To this stirred mixture is added dropwise over a period of 15 minutes 44.0 grams (0.17 mole) of a 70% aqueous solution of 2,4,6-trimethylol phenol. There is no apparent temperature change. The reaction mixture is then heated to C., refluxed 45 minutes, and 24 milliliters of water is collected (the calculated amount of water is 22 milliliters). The product is a dark brown liquid (as a 68% xylene solution).
Example 2d This example illustrates the reaction of a methylol diphenol.
One mole of substantially water-free and 4 moles of triethylenetetramine in 300 m1. of xylene are mixed with stirring. Although an exothermic reaction takes place during the mixing, the temperature is maintained below 60 C. The reaction mixture is then heated and azeotroped until the calculated amount (72 g.) of water is removed (4 moles of water of reaction). The maximum temperature is C. and the total reaction time is 8 hours. Xylene is then removed under vacuum. The product is a viscous water-soluble liquid.
Example 5 b In this example, 1 mole of substantially water-free is reacted with 2 moles of Duomeen S (Armour Co.),
where R is a fatty group derived from soya oil, in the manner of Example 2a. Xylene is used as both solvent and azeotroping agent. The reaction time is 8 hours and the maximum temperature ISO-160 C.
Example 28b This experiment is carried out in the same equipment as is employed in Example 28a except that a 300 milliliter flask is used. Into the flask is placed 50 grams of xylene and 8.4 grams (0.05 mole) of 2,6-dimethylol-4- methylphenol are added. The resulting slurry is stirred and warmed up to 80 C. Polyamine N400, 40.0 grams (0.10 mole) is added slowly over a period of 45 minutes. Solution takes place upon the addition of the polyamine. The reaction mixture is refluxed for about 4 hours at 140 C. and 1.8 milliliters of water is collected, the calculated amount. The product, as a xylene solution, is a brown liquid.
Example 29b This experiment is carried out in the same equipment and in the same manner as is employed in Example 2812. To a slurry of 10.5 grams (0.05 mole) of 2,6-dimethylol- 4-tertiarybutylphenol in 50 grams of xylene, 40 grams (0.10 mole) of Polyamine N-400 are added all at once with stirring and the mixture is heated and refluxed at 140 C. for 4 hours with the collection of 1.6 milliliters of water. The calculated amount of water is 1.8 milliliters. The product, as a xylene solution, is reddish brown.
Example 30b This experiment is carried out in the same equipment and in the same manner as is employed in Example 28b. To a slurry of 14.0 grams of 2,6-dimethylol-4-nonylphenol in 50 milliliters of benzene, 40.0 grams (0.10 mole) of Polyamine N-400 are added all at once with stirring and the mixture is heated and refluxed at 140 C. for 6 hours with the collection of 1.8 milliliters of water. 'The calculated amount of water is 1.8 milliliters. The product, as a xylene solution, is dark brown.
The following amino-methylol condensates shown in Tables I-IV are prepared in the manner of Examples 1a, 2d, and 5b. In each case one mole of polyamine per equivalent of methylol group on the phenol is reacted and the reaction carried out until, taking into consideration the water originally present, about one mole of water is removed for each equivalent of methylol group present on the phenol.
The pH of the reaction mixture is determined solely by the reactants (i.e., no inorganic base, such as Ca(OH) NaOH, etc. or other extraneous catalyst is present). Examples 1a, 2d, and 5b are also shown in the tables. Attempts are made in the examples to employ commercially available materials where possible.
In the following tables the examples will be numbered by a method which will describe the nature of the prodnot. The polyamine-methylol condensate will have a basic number, for example, 1a, 4b, 6c, 4d, wherein those in the A series are derived from TMP, the B series from DMP, the C series from trimethylol cardanol and side chain hydrogenated cardanol (i.e., hydrocardanol), and the d series from the tetramethylol diphenols. The basic number always refers to the same amino condensate. The symbol A before the basic number indicates that the polyamine had been acylated prior to condensation. The symbol A after the basic number indicates that acylation takes place after condensation.
A25a means that the 25a (amino condensate) was prepared from an amine which had been acylated prior to condensation. However, 10aA means that the condensate was acylated after condensation. The symbol 0 indicates oxyalkylation. Thus 10aAO indicates that the amine condensate 10a has been acylated (IOaA), followed by oxyalkylation. IOaAOA means that the same condensate, 10a, has been acylated (1042A), then oxyalkylated (IOaAO) and then acylated. In other words, these symbols indicate both kind and order of treatment.
Reaction TABLE I HOOH 0H2OH (designated TM P) and polyamines Hz 0 H [Molar ratio TMP to amine 1 :3]
Polyamine Diethylene triamine.
Triethylene tetramine.
'letraethylene pentamine. Dipropylene triamine.
H Duomeen S (Armour Co.) RN-CHzCHzCHzNH R derived from soya oil H Duomeen T (Armour Co.) RN-CHzCHzCH2NHg R derived from tallow Oxyethylated Duomeen S C2H4OH Oxyethylated Duomeen T C2H4OH N-methyl ethylene diamine.
N ,N-dimetl1yl ethylene diamine. Hydroxyethyl ethylene diamine. N,N-dihydroxyethylethylene diamine. N-methyl propylene diamine. N,N-dihydroxyethy1 propylene dia mne. N,N-dihydroxypropyl propylene diamine.
TABLE IVCntinued The products formed in the above Table III are dark, viscous liquids.
TABLE IV Reaction of I R I (Tetramethylol diphenol) with HO ([3 -OH polyamine I R CHzOH CHZOH [Molar ratio of tetramethylol diphenol to polyamine 1:4]
Example R Polyaniiue Hydrogen Diethylene trial-nine. do Triethylene tetramine.
Tetraethylene pentamine. Dipropylene triamine. Duomeen S (Armour O0.)
R derived from soya oil Dipropylene triamine. Duomeen S (Armour C0.)
R derived from soya oil Example R Polyamine 18d Methyl Duomeen T (Armour 00.)
H RNCH2CH2CH2NH2 R derived from tallow 19d do Oxyethylated Duomeen S C2H4OH RCHzCH2OHzN 20d do Oxyethylated Duomeen T C2H4OH R l %OH CHzCH2N 21d do Amine ODT (Monsanto) H 12 z5gC2H4NC2H4HNz 22d do Oxyethylated Amine ODT CzHiOH O 2H25IE [T-C H -O2HiN 23d d0 N-(2-hydroxyethyl)-2-methyl-l,2-propanedi- 24a "do N i i iiiyl ethylene diamine.
The products formed in the above Table IV are dark, viscous liquids.
THE ACYLATING AGENT As in the reaction between the methylol phenol and the secondary amine, acylation is also carried out under dehydrating conditions, i.e., water is removed. Any of the well-known methods of acylation can be employed. For example, heat alone, heat and reduced pressure, heat in combination with an azeotroping agent, etc., are all satisfactory.
A wide variety of acylating agents can be employed. However, strong acylating agents such as acyl halides, or acid anhydrides should be avoided since they are capable of esterifying phenolic hydroxy groups, a feature which is undesirable.
Although a wide variety of carboxylic acids produce excellent products, in our experience monocarboxy acids having more than 6 carbon atoms and less than 40 carbon atoms give most advantageous products. The most common examples include the detergent forming acids, i.e., those acids which combine with alkalies to produce soap or soap-like bodies. The detergent-forming acids, in turn, include naturally-occurring fatty acids, resin acids, such as abietic acid, naturally occurring petroleum acids, such as naphthenic acids, and carboxy acids, produced by the oxidation of petroleum. As will be subsequently indicated, there are other acids which have somewhat similar characteristics and are derived from somewhat different sources and are different in structure, but can be included in the broad generic term previously indicated.
Suitable acids include straight chain and branched chain, saturated and unsaturated, aliphatic, alicyclic, fatty, aromatic, hydroaroinatic, and aralkyl acids, etc.
Examples of saturated aliphatic monocarboxylic acids are acetic, propionic, butyric, valeric, caproic, heptanoic, caprylic, nonanoic, capric, undecanoic, lauric, tridecanoic, myristic, pentadecanoic, palmitic, heptadecanoic, stearic, nonadecanoic, eicosanoic, heneicosanoic, docosanoic, tricosanoic, tetracosanoic, pentacosanoic, cerotic, heptacosanoic, montanic, nonacosanoic, melissic and the like.
Examples of ethylenic unsaturated aliphatic acids are acrylic, methacrylic, crotonic, angelic, tiglic, the pentenoic acids, the hexenoic acids, for example, hydrosorbic acid, the heptenoic acids, the octenoic acids, the nonenoic acids,
the decenoic acids, for example, obtusilic acid, the undecenoic acids, the dodccenoic acids, for example, lauroleic, linderic, etc., the tridecenoic acids, the tetradecenoic acids, for example, myristoleic acid, the pentadecenoic acids, the hexadecenoic acids, for example, palmitcleic acid, the heptadecenoic acids, the octodecenoic acids, for example, petrosilenic acid, oleic acid, elardic acid, the nonadecenoic acids, for example, the eicosenoic acids, the docosenoic acids, for example, erucic acid, brassidic acid, cetoleic acid, the tetracosenoic acids, and the like.
Examples of dienoic acids are the pentadienoic acids, the hexadienoic acids, for example, sorbic acid, the octadienoic acids, for example, linoleic, and the like.
Examples of the trienoic acids are the octadecatrienoic acids, for example, linolenic acid, eleostearic acid, pseudoeleostearic acid, and the like.
Carboxylic acids containing functional groups such as hydroxy groups can be employed. Hydroxy acids, particularly the alpha hydroxy acids include glycolic acid, lactic acid, the hydroxyvaleric acids, the hydroxy caproic acids, the hydroxyheptanoic acids, the hydroxy caprylic acids, the hydroxynonanoic acids, the hydroxycapric acids, the hydroxydecanoic acids, the hydroxy lauric acids, the hydroxy tridecanoic acids, the hydroxymyristic acids, the hydroxypentadecanoic acids, the hydroxypalmitic acids, the hydroxyhexadecanoic acids, the hydroxyheptadecanoic acids, the hydroxy stearic acids, the hydroxyoctadecenoic acids, for example, ricinoleic acid, ricinelardic acid, hydroxyoctadecenoic acids, for example, ricinstearolic acid, the hydroxyeicosanoic acids, for example, bydroxyarachidic acid, the hydroxydocosanoic acids, for example, hydroxybehenic acid, and the like.
Examples of acetylated hydroxyacids are ricinoleyl lactic acid, acetyl ricinoleic acid, chloroacetyl ricinoleic acid, and the like.
Examples of the cyclic aliphatic carboxylic acids are those found in petroleum called naphthenic acids, hydnocarbic and chaulmoogric acids, cyclopentane carboxylic acids, cyclohexanecarboxylic acid, campholic acid, fencholic acids, and the like.
Examples of aromatic monocarboxylic acids are bcnzoic acid, substituted benzoic acids, for example, the toluic acids, the xylenic acids, alkoxy benzoic acid, phenyl benzoic acid, naphthalene carboxylic acid, and the like.
Mixed higher fatty acids derived from animal or vegetable sources, for example, lard, coconut oil, rape-seed oil, sesame oil, palm kernel oil, palm oil, olive oil, corn oil, cottonseed oil, sardine oil, tallow, soyabean oil, peanut oil, castor oil, seal oils, whale oil, shark oil, and other fish oils, teaseed oil, partially or completely hydrogenated animal and vegetable oils are advantageously employed. Fatty and similar acids include those derived from various waxes, such as beeswax, spermaceti, montan wax, Japan wax, coccerin and carnauba Wax. Such acids include carnaubic acid, cerotic acid, lacceric acid, montanic acid, psyllastearic acid, etc. One may also employ higher moleular weight carboxylic acids derived by oxidation and other methods, such as from paraffin wax, petroleum and similar hydrocarbons; resinic and hydroaromatic acids, such as hexahydrobenzoic acid, hydrogenated naphthoic, hydrogenated carboxy diphenyl, naphthenic, and abietic acid; Twitchell fatty acids, carboxydiphenyl pyridine carboxylic acid, blown oils, blown oil fatty acids and the like.
Other suitable acids include phenylstearic acid, benzoyi nonylic acid, cetyloxybut ric acid, cetyloxyacetic acid, chlorstearic acid, etc.
Examples of the polycarboxylic acids are those of the aliphatic series, for example, oxalic, malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic, nonanedicarboxylic acid, decanedicarboxylic acids, undecanedicarboxylic acids, and the like.
Examples of unsaturated aliphatic polycarboxylic acids 22 are fumaric, maleic, mesacenic, citraconic, glutaconic, itaconic, muconic, aconitic acids, and the like.
Examples of aromatic polycarboxylic acids are phthalic, isophthalic acids, terephthalic acids, substituted derivatives thereof (e.g. alkyl, chloro, alkoxy, etc. derivatives), biphenyldicarboxylic acid, diphenylether dicarboxylic acids, diphenylsulione dicarboxylic acids and the like.
Higher aromatic polycarboxylic acids containing more than two carboxylic groups are hemirnellitic, trimellitic, trimesic, mellophanic, prehnitic, pyromellitic acids, mellitic acid, and the like.
Other polycarboxylic acids are the dimeric, trimeric and polymeric acids, for example, dilinoleic, trilinoleic, and other polyacids sold by Emery industries, and the like. Other polycarboxylic acids include those containing other groups, for example, diglycolic acid. Mixtures of the above acids can be advantageously employed.
In addition, acid precursors such as esters, glyccrides, etc. can be employed in place of the tree acid.
The moles of acylating agent reacted with the polyarninomethyl compound will depend on the number of acetylation reactive positions contained therein as well as the number of moles one Wishes to incorporate into the molecule. We have advantageously reacted 1 to 15 moles of acylating agent per mole of polyaminophenol, but preferably 3 to 6 moles.
The following examples are illustrative of the preparation of the acylated polyaminomethyl phenol condensate.
The following general procedure is employed in acylating. The condensate is mixed with the desired ratio of acid and a suitable azeotroping agent is added. Heat is then applied. After the removal of the calculated amount of Water (1 to 2 equivalents per mole of acid employed), heating is stopped and the azeotroping agent is evaporated under vacuum. The temperature during the reaction can vary from 200 C. (except where the formation of the cyclic amidine type structure is desired and the maximum temperature is generally 200280). The times range from 4 to 24 hours. Here again, the true test of the degree of reaction is the amount of Water removed.
Example 30.4
In a 5 liter, 3 necked fiask furnished with a stirring device, thermometer, phase separating trap, condenser and heating mantle, 697 grams of 3a (one mole of the TMP-tetraethylene pentamine reaction product) is dissolved in 600 ml. of xylene. 846 grams of oleic acid (3 moles) is added to the TMP-polyamine condensate with stirring in ten minutes. The reaction mixture was then heated gradually to about in half an hour and then held at about over a period of 3 hours until 54 grams (3 moles) of. water is collected in the side of the tube. The solvent is then removed with gentle heating under a reduced pressure of approximately 20 mm. The product is a dark brown viscous liquid with a nitrogen content of 14.5%.
Example SaA The prior example is repeated except that the final reaction temperature is maintained at 240 C. and 90 grams (5 moles) of water is removed instead of 54 grams. Infrared analysis of the product indicates the presence of a cyclic amidine ring.
Example 7aA The reaction product of Example 7a (TMP and oxyethylated Duomeen S) is reacted with palmitic acid in the manner of Example 311A. A xylene soluble product is formed.
The following examples of acylated polyaminomethyl phenol condensates are prepared in the manner of the above examples. The products obtained are dark viscous liquids.
Example 28aA Into a 300 milliliter flask, fitted with a stirring device,
thermometer, phase separating trap, condenser and heating mantle, is placed a xylene solution of the product of Example 28a containing 98.0 grams (0.05 mole) of the reaction product of 2,4,6-trimethylolphenol and Polyamine N400 and about 24 grams of xylene. To this. solution is added with stirring 30.0 grams (0.15 mole) of lauric acid. The reaction mixture is heated for about one hour at a maximum reaction temperature of 190 C. and 6 milliliters of water are collected. The calculated amount of water for imidazoline formation is 5.4 milliliters. The resulting product as an 88 percent Xylene solution is a dark brown thick liquid.
Example 2817A Into a 300 milliliter flask, fitted with a stirring device, thermometer, phase separating trap, condenser and heating mantle is placed a xylene solution of the product of Example 28!) containing 35.0 grams (0.025 mole) of the reaction product of 2,6-dimethylol-4-methylphenol and Polyamine N400 and about 20 grams of Xylene. To this solution is added with stirring 14.1 grams (0.05 mole) of oleic acid. The reaction mixture is heated at reflux for 4.5 hours at a maximum temperature of 183 C. and 1.0 milliliters of Water is collected, the calculated amount of Water for amide formation being 0.9 milliliter. The product is a dark burgundy liquid (as 70.5% xylene solution was brown. Example 29bA This experiment is performed in the same equipment and in the same manner as employed in Example 28bA. Into the flask is placed a xylene solution of the product of Example 291) containing 40.9 grams (0.025 mole) of the reaction product of 2,6-dimethylol-4-tertiarybutyl phenol and Polyamine N-400 and about 47 grams of xylene. To this solution is added With stirring 7.2 grams (0.05 mole) of octanoic acid. The reaction mixture is heated at reflux for 3.75 hours at a maximum temperature of 154 C. and 1.3 milliliters of water is collected. The calculated amount of Water for amide formation is 0.9 milliliter. The product as a 49.82 percent xylene solu- This experiment is performed in the same manner and in the same equipment as is employed in Example 2811A. Into the flask is placed a xylene solution of the product of Example 30b containing 39.6 grams (0.025 mole) of the reaction product of 2,6 dimethylol-4-nonylphenol and Polyamine N400 and about 32 grams of xylene. To this solution is added with stirring 14.2 grams (0.05 mole) of stearic acid. The reaction mixture is heated at reflux for 4 hours at a maximum temperature of 160 C. and 1.0 milliliter of Water is collected. The calculated amount of water for amide formation is 0.9 milliliter. The product as a 62.5% xylene solution is a brown liquid.
TABLE V.ACYLATED PRODUCTS or TABLE I 1 Dilinoleic acid sold by Emery Industries. {Naphthenic acid sold by Sun Oil Company, average molecular Weight 220-230.
TABLE VI.--ACYLATED PRODUCTS 013 TABLE II Grams of acid used Grams of Example Acid per gramwater mole of removed condensate Stearie 568 36 564 36 800 '72 120 36 456 36 512 36 Dimerie 1, 200 36 Oleic 564 36 d 564 36 660 36 564 36 564 36 512 36 240 72 564 36 1, 128 72 a. 564 36 564 36 400 36 564 40 288 52 Stearic 569 40 See footnotes 1 and 2, Table V.
Grams of acid used Grams of water removed Acid Example See footnotes 1 & 2, Table V.
TABLE VIII.ACYLATED PRODUCTS OF TABLE IV Grams of acid used Grams of Example Acid per gramwater mole of removed condensate See footnotes 1 and 2, Table V.
Reference has been made and reference will be continued to be made herein to oxyalkylation procedures. Such procedures are concerned with the use of monoepoxides and principally those available commercially at low cost, such as ethylene oxide, propylene oxide and butylene oxide, octylene oxide, styrene oxide, etc.
Oxyalkylation is well known. For purpose of brevity reference is made to Parts 1 and 2 of US. Patent 'No. 2,792,371, dated May 14, 1957, to Dickson in which par- 25 ticular attention is directed to the various patents which describe typical oxyalkylation procedure. Furthermore, manufacturers of alkylene oxides furnish extensive in formation as to the use of oxides. For example, see the technical bulletin entitled Ethylene Oxide which has been distributed by the Jefferson Chemical Company, Houston, Texas. Note also the extensive bibliography in this bulletin and the large number of patents which deal with oxyalkylation processes.
The following examples illustrate oxyalkylation.
Example 111/10 The reaction vessel employed is a 4 liter stainless steel autoclave equipped with the usual devices for heating and heat control, a stirrer, inlet and outlet means, etc., which are conventional in this type of apparatus. The stirrer is operated at a speed of 250 rpm. Into the autoclave is charged 1230 grams (1 mole) of MA, and 500 grams of xylene. The autoclave is sealed, swept with nitrogen, stirring started immediately, and heat applied. The temperature is allowed to rise to approximately 100 C. at which time the addition to ethylene oxide is started. Ethylene oxide is added continuously at such speed that it is absorbed by the reaction mixture as added. During the addition 132 grams (3 moles) of ethylene oxide is added over 2% hours at a temperature of 100 C. to 120 C. and a maximum pressure of 30 p.s.i.
Example laAO The reaction mass of Example 1A0 is transferred to a larger autoclave (capacity 15 liters) similarly equipped. Without adding any more xylene the procedure is repeated so as to add another 264 grams (6 moles) of ethylene oxide under substantially the same operating conditions but requiring about 3 hours for the addition.
Example /10;
In a third step, another 264 grams (6 moles) of ethylene oxide is added to the product of Example 1aAO The reaction slows up and requires approximately 6 hours, using the same operating temperatures and pressures.
Example 10/10 The reaction vessel employed is the same as that used in Example laAO. Into the autoclave is charged 1230 g. (1 mole) of laA and 500 grams of xylene. The autoclave is sealed, swept with nitrogen, stirring is started immediately, and heat is applied. The temperature is allowed to rise to approximately 100 C. at which time the addition of propylene oxide is started. Propylene oxide is added continuously at such speed that it is absorbed by the reaction mixture as added. During the addition 174 g. (3 moles) of propylene oxide are added over 2 hours at a temperature'of 100 to 120 C. and a maximum pressure of 30 lbs. p.s.i.
Example 152/10 The reaction mass of Example 1aAO is transferred to a larger autoclave (capacity liters). The procedure is repeated so as to add another 174 g. (3 moles) of propylene oxide under substantially the same operating conditions but requiring about 3 hours for the addition.
Example IaAO At the end of the second step (Example 1aAO the autoclave is opened, g. of sodium methylate is added,
26 and the autoclave is flushed out as before. Oxyalkylation is continued as before until another 522 g. (9 moles) of propylene oxide are added. 8 hours are required to complete the reaction.
The following examples of oxyalkylation are carried out in the manner of the examples described above. A catalyst is used in the case of oxyethylation after the initial 15 moles of ethylene oxide are added, while in the case of oxypropylation, the catalyst is used after the initial 6 moles of oxide are added. In the case of oxybutylation, oxyoctylation, oxystyrenation, etc. the cata lyst is added at the beginning of the operation; In all cases the amount of catalyst is about 1 percent of the total reactant present. The oxides are added in the order given reading from left to right. The results are presented in the following tables:
[Grams of oxide added per gram-mole of condensate] Example EtO PrO BuO Octylcne oxide Styrene oxide [Grams of oxide added per gram-mole of condensate] Example PrO BuO Octylene oxide Styrene EtO . oxide TABLE XI.THE OXYALKYLATED PRODUCTS OF TABLE III [Grams of oxide added per gram-mole oi condensate] Example EtO PrO B Octylene oxide l 27 as l TABLE XII.THE OXYALKYLATED PRODUCTS OF TABLE XVI.THE OXYALKYLATE D PRODUCTS TABLE IV OF TABLE VII [Grams of oxide added per gram-mole of condensate] [Grams of oxide added per gram-mole of aeylated product] 1 Example Eto Pr 0 Buo 83 52 gg g 5 Example EtO PrO BuO Octyleue Styrene oxide oxide TABLE XIII.THE OXYALKYLATED PRODUCTS OF TABLE V [Grams of oxide added per gram-mole of condensate] Example EtO PrO BuO Oetylene Styrene 2a oxide oxide Since the oxyalkylated, and the acylated and oxyalkylated prducts have terminal hydroxy groups, they can be gig: "j: acylated. This step is carried out in the manner pre- :{aigz viously described for acylation. These examples are illustrative and not limiting.
Example IaOA One mole (919 grams) of MO mixed with 846 grams (three moles) of oleic acid and 300 ml. xylene. The reaction mixture is heated to about 150160 C. over a period of 2 hours until 54 grams (3 moles) of Water are removed. Xylene is then removed under vacuum. The product laOA is xylene soluble.
Example JaAOA TABLE XIV.THE OXYALKYLATED PRODUCTS OF TABLE VI The process of the immediately previous example is re- [Gramsofoxide added pe gram-mole ofacylated p 45 peated using laAO. The product laAOA is xylene soluble. Exam le EtO PrO BuO Oct lene St ene p g $316 Additional examples are presented in the following tables. All of the products are dark, viscous liquids.
TABLE XVII.THE AOYLATEDXIIIRODUCTS OF TABLES IX Grams of acid per Grams gram-mole Water Example Acid 01' oxyalkylremoved ated product TABLE XV.-THE OXYALKYLATED PRODUCTS OF TABLE VI 232 [Grams of oxide added per gram-mole of aeylated product] 282 Example EtO PrO Oetylene Styrene oxide anaenss TABLE XVIIL-THE ACYLAIED PRODUCTS OF TABLES XIII, XIV, XV, XVI
(1) BREAKING AND PREVENTING WATER-IN- OIL EMULSIONS This phase of our invention relates to the use of oxyalkylated and other products of the present invention in preventing, breaking or resolving emulsions or" the waterin-oil type, and particularly petroleum emulsions. Their use provides an economical and rapid process for resolving petroleum emulsions of the water-in-oil type that are commonly referred to as cut oil, roily oil, emulsified oil, etc., and which comprise fine droplets of naturallyoccurring waters or brines dispersed in a more or less permanent state throughout the oil which constitutes the continuous phase of the emulsion.
They also provide an economical and rapid process for separating emulsions which have been prepared under controlled conditions from mineral oil, such as crude oil and relatively soft waters or weak brines. Controlled emulsification and subsequent demulsification, under the conditions just mentioned, are of significant value in removing impurities, particularly inorganic salts, from pipeline oil (i.e. desalting).
Demulsification, as contemplated in the present application, includes the preventive step of commingling the demulsifier with the aqueous component which would or might subsequently become either phase of the emulsion in the absence of such precautionary measure. Similarly, such demulsifier may be mixed with the hydrocarbon component.
These demulsifying agents employed in the treatment of oil field emulsions are used as such, or after dilution with any suitable solvent, such as Water, petroleum hydrocarbons, such as benzene, toluene, xylene, tar acid oil, cresol, anthracene oil, etc. Alcohols, particularly aliphatic alcohols, such as methyl alcohol, ethyl alcohol, denatured a1- cohol, propyl alcohol, butyl alcohol, hexyl alcohol, octyl alcohol, etc., are often employed as diluents. Miscellaneous solvents, such as pine oil, carbon tetrachloride, sulfur dioxide extract obtained in the refining of petroleum, etc., are often employed as diluents. Similarly, the material or materials employed as the demulsifying agent of our process are often admixed with one or more of the solvents customarily used in connection with conventional demulsifying agents. Moreover, said material or materials are often used alone or in admixture with other suitable well-known classes of demulsifying agents.
These demulsifying agents are useful in a water-soluble form, or in an oil-soluble form, or in a form exhibiting both oil and water-solubility. Sometimes they are used in a form which exhibits relatively limited oil-solubility. However, since such reagents are frequently used in a ratio of 1 to 10,000, or 1 to 20,000, or 1 to 30,000, or even 1 to 40,000, or 1 to 50,000, as in desalting practice,
' such an apparent insolubility in oil and Water is not sigsifying agent of the kind above described is brought into contact with or caused to act upon the emulsion to be treated, in any of the various apparatus now generally used to resolve or break petroleum emulsions with a chemical reagent, the above procedure being used alone or in combination with other demulsifying procedure, such as the electrical dehydration process.
One type of procedure is to accumulate a volume of emulsified oil in a tank and conduct a batch treatment type of demulsification procedure to recover clean oil. In this procedure the emulsion is admixed with the demulsifier, for example by agitating the tank of emulsion and slowly dripping demulsifier into the emulsion. In some cases mixing is achieved by heating the emulsion while dripping in the demulsifier, depending upon the convection currents in the emulsion to produce satisfactory admixture. In a third modification of this type of treatment, a circulating pump withdraws emulsion from, e.g. the bottom of the tank, and re-introduces it into the top of the tank, the demulsifier being added, for example, at the suction side of said circulating pump.
In second type of treating procedure, the demulsifier is introduced into the well fluids at the well-head or at some point between the well-head and the final oil storage tank, by means of an adjustable proportioning mechanism or proportioning pump. Ordinarily the flow of fluids through the subsequent lines and fittings suffices to produce the desired degree of mixture of demulsifier and emulsion, although in some instances additional mixing devices may be introduced into the flow system. In this general procedure, the system may include various mechanical devices for withdrawing free water, separating entrained water, or accomplishing quiescent settling of the chemicalized emulsion. Heating devices may likewise be incorporated in any of the treating procedures described herein.
A third type of application (down-the-hole) of demulsifier to emulsion is to introduce the demulsifier either periodically or continuously in diluted or undiluted form into the well and to allow it to come ot the surface with the well fluids, and then to flow the chemicalized emulsion through any desirable surface equipment, such as employed in the other treating procedures. This particular type of application is decidedly useful when the demulsifier is used in connection with acidification of calcareous oil-bearing strata, especially if suspended in or dissolved in the acid employed for acidification.
In all cases, it will be apparent from the foregoing description, the broad process consists simply in introducing a relatively small proportion of demulsifier into a relatively large proportion of emulsion, admixing the chemical and emulsion either through natural flow or through special apparatus, with or without the application of heat, and allowing the mixture to stand quiescent until the desirable water content of the emulsion separates and settles from the mass.
The following is a typical installation:
A reservoir to hold the demulsifier of the kind described (diluted or undiluted) is placed at the well-head where the effluent liquids leave the well. This reservoir or container, which may vary from 5 gallons to 50 gallons for convenience, is connected to a proportioning pump which injects the demulsifier drop-wise into the fluids leaving the well. Such chemicalized fluids pass through the flowline into a settling tank. The settling tank consists of a tank of any convenient size, for instance, one which will hold amounts of fluid produced in 4 to 24 hours (500 barrels to 2000 barrels capacity), and in which there is a perpendicular conduit from the top of the tank to almost the very bottom so as to permit the incoming fluids to sa tsies pass from the top of the settling tank to the bottom, so that such incoming fluids do not disturb stratification which takes place during the course of demulsification. The settling tank has two outlets, one being below the Water level to drain off the water resulting from demulsification or accompanying the emulsion as free water, the other being an outlet at the top to permit the passage of dehydrated oil to a second tank, being a storage tank, which holds pipeline or dehydrated oil. If desired, the conduit or pipe which serves to carry the fluids from the well to the settling tank may include a section of pipe with baflles to serve as a mixer, to insure thorough distribution of the demulsifier throughout the fluids, or a heater for raising the temperature of the fluids to some convenient temperature, for instance, 120 to 160 F., or both heater and mixer.
Demulsification procedure is started by simply setting the pump so as to feed a comparatively large ratio of demulsifier, for instance, 1:5,000. As soon as a complete break or satisfactory demulsification is obtained, the pump is regulated until experience shows that the amount of demulsifier being added is just sufl'icient to produce clean or dehydrated oil. The amount being fed at such stage is usually 1210,000, 1: 15,000, 1220,000, or the like. However, with extremely difficult emulsions higher concentrations of demulsifier can be'employed.
' In many instances the oxyalkylated products herein specified as demulsifiers can be conveniently used without dilution. However, as previously noted, they may be diluted as desired with any suitable solvent. Selection of the solvent will vary, depending upon the solubility characteristics of the oxyalkylated product, and, of course will be dictated in part by economic consideration, i.e., cost. The products herein described are useful not only in diluted form but also admixedwith other chemical demulsifiers.
In recent years pipeline standards for oil have been raised so that an effective demulsifier must not only be able to break oil field emulsions under conventional conditions without sludge, but at the same time it must also yield bright pipeline oil, i.e., pipeline oil that is free from the minute traces of foreign matter, whether suspended water or suspended emulsion droplets due to nonresolvable solids. In addition the water phase should be free of oil so as not to create a disposal problem. Thus it is presently desirable to use a demulsifier that produces absolutely bright, haze-free oil in the top layer, yields little or no interphas edsludge, and has little if any oil in the Water phase. 7 V
The following examples show results obtained in the resolution of crude petroleum emulsions obtained from various sources. 7
Examples This example illustrates the use of a product of the kind presently described for the demulsification of a Texas type oil which is'unusually resistant to treatment. The particular demulsification agent employed is that of Example 1A-l. The operating conditions are as employed in conventional treatment (see US. Patent 2,626,929 to De Groote). On this particular lease, (Cobb lease Well #4 of the Texas Company, West Andrews, Texas) one part of demulsifier resolves approximately 10,000 parts of emulsion. The emulsion represents about 60% oil and 40% water. The oil produced is very bright, shows a minimum of residual impurities, and the draw-off water is absolutely clear by visual inspection. No heat is applied in the treating process.
Similarly effective demulsification is effected by em ploying the compounds shown in the following table. The emulsions are taken from the following leases:
(1) Gulf Oil Company, Goose Creek, Texas, Hurst Station Lease, Well #13, water.
PETROLEUM WATER/OIL DEMULSIFIERS 2a (568)+stearic acid (852) 54 (5 0 2a (568)+stearic acid (852) 72 (A)PIO(614470) (B)Et.O(l6300) 2a (568)+stearic acid (852); lb (492)+oleic acid (564). 1b (492)+oleic acid (564). 1b (492)-l-oleie acid (564). 1c (G45)+1auric acid (600) 10 (645H-lauric acid (600).
2 54 (A) PrO(48620) (BgEtO (5560) 54 (A) PIO(48620) (B)Et0(9320) 3c (907)-1-lauric acid (600) 28b (1400)+olcic acid (564)".-- 9b (1635) b (1580)+st1caric acid (569) 30 (907) +1auric acid (600) 54 (A) Pro (04520) (B) E170 (20440) 1(1 (660)+1auric acid (800) 72 A PIO(\9400) (B)EtO(20820) 1d (660)+1auric acid (800) 108 (A)Pr0(54080) (B)Et0(13520 1d (660)+lauric acid (800) 108 (A) Pr0(67600) (B)EtO(l7580) 2sc 19eo +icuiic. (600)-... 120 (A)P!O(17560) (B)Et0(13630) 28a 1900 +lau1ic acid 600) 120 28a0 (3054)+stearic acid (284) 1s 28aAOA 28b (1400) (A)Pr0(47640) (B)Et0(a950) 28b (1400)+olcic acid (564) (A)Bu0(l7040) (B) Et0(5680) (A)Bu0(780) (B) P!O(1264) (C) EtO(7720) (A) PrO (40000) (B) EtO (15000) (A)EDO (1095) (B) 11'0 (12000) (2) Texas Company, Pierce Junction, Texas, Oden Lease Well #3, 45% Water.
(3) Delhi-Taylor Oil Company, Berclair, Texas, Lutenbeck Lease, Well #9, 20% water.
(4) Sun Oil Company, Andrews, Texas, Means A Lease, 5% water.
(5) Shell Oil Company, Loop, Texas, Williamson Lease, Well #1, 35% water.
(6) General Petroleum Company, Wilmington, California, Southern Pacific Lease.
(7) Richfield Oil Company, North Coles Lease, Section A.
(8) Shell Oil Company, Brea, California, Puente Lease.
(9) Southwest Oil Company, Huntington Beach, California, TF #1, Wells 5 and 6.
(l0) Morton Kolgush Company, Torence, California, Well #7, Redondo Beach, California.
The unexpectedness of this phase of the present invention is demonstrated since the above emulsions are ordinarily not susceptible to cationic and cryptocationic demulsifiers. The present compounds give better results, more rapid demulsification, clearer oil, cleaner draw-off water and more complete absence of sludge than other cationic demulsifiers tried. The demulsifiers prepared by reacting the methylol phenol With the polyamine and then oxyalkylating the condensate are particularly effective. For example, those products obtained by reacting one mole of TMP with three moles of diethylene triarnine, triethylene tetramine or tetraethylene pentamine and then subjecting them to oxyalkylation involving the use of both ethylene and propylene oxides, preferably propylene oxide first, in the same Weight ratio (i.e. equal Weight of alkylene oxide to amine condensate) as employed in the oxyalkylation of certain polyamines described in US. Patents 2,792,369-373, show effectiveness in ratios of from 1:10,000 to 130,000 or higher ratios on oils of the kind available in the Puente Lease, the Southwest Oil Lease, the Morton Kolgush Co. Lease, etc. mentioned above.
Because of their demulsification properties the compounds are also useful in preventing the formation of emulsions during transit.
Often oil Which meets specifications when shipped a-rrives emulsified at its destination when extraneous water becomes mixed with the oil during transit through pipe lines, storage in tanks during transportation in seagoing tankers, and the like.
For example, as is Well known in a number of plaecs where petroleum is produced containing a minimum amount of foreign matter and is completely acceptable for refiner ypurposes prior to shipment, it is not acceptable after a shipment has been made, for instance, thousands of miles by tanker. The reason is that an empty tanker employs sea water for ballast prior to reloading and it is almost impossible to remove all ballast sea water before the next load starts. In some instances a full tanker may use sea Water for ballast also. In other instances, due to seepage, etc., contamination takes place. The rolling or rocking effect of the sea voyager seems to give all the agitation required. It is to be noted that the emulsion, generally a Water-in-oil type, so produced is characterized by the fact that the dispersed phase is sea water.
Typical examples are shipments of oil from the Near East to Japan, Australia, etc., and various quantities shipped to the west coast of the USA. and, for that matter, to the east coast of the USA.
The presence of Water in petroleum distillate fuels often results in emulsion formation especially when such Water-containing fuels are subjected to agitation or other conditions promoting emulsification. Unless such emulsion formation is retarded or emulsions that have been formed are resolved so as to permit separation of water from the fuel, the water entering the fuel system deleteriously affects the performance of the system, particu- 34 larly mechanisms therein of ferrous metals With which the water-containing fuel comes into contact.
As an example, serious difficulties arise in marine operations when salt water, in amounts even as low as 0.01% by weight of a diesel fuel, enters diesel engines. The presence of Water in the fuel enhances emulsification thereof and some of the emulsion normally passes through filtering media in the same manner as the fuel that has not been emulsified and, as a result, rapid engine failures often occur. Such failures are often due to corrosion of metal surfaces, as is manifested by surface pitting and formation of fatigue cracks on machined parts, to deleterious effects on fuel injectors resulting in broken or completely disintegrated check valve springs, to promotion of seizure of plungers in bushings and general corrosion of metal surfaces that are contacted by the Water-containing fuel. Accordingly, the presence of Water in petroleum distillate fuels, and particularly in diesel fuels, is highly undesirable and means are generally employed to separate the Water, often in emulsified form, from the fuel. When the Water present in the fuel oil is in emulsified form, one method for treating the emulsion to prevent water from entering the system is to break the emulsion and separate water from the fuel. As manufactured, petroleum distillates suitable for use as fuels are normally water free or contain not more than a trace of Water and, hence, such distillates per se present little, if any, difficulty from emulsification unless extraneous water becomes admixed therewith.
In illustration reference is made to a current Navy Department Specification for diesel fuels which, in listing the chemical and physical requirements for conformance therewith, sets forth that the diesel fuels must not contain more than a trace, as a maximum, of water and sediment. Nevertheless, and in the handling of such fuels through pipe lines, storage thereof in tanks, and during transportation such as in seagoing tankers, eX- traneous water oftentimes becomes admixed with the fuel thereby providing difiiculties inclusive of those aforesaid.
Oil in transit can be effectively inhibited against emulsification by adding a small amount, i.e., sufiicient substantially to reduce the tendency of the fuel to emulsify, of the demulsifiers described above.
In practicing this phase of our invention, the contemplated demulsifiers may be added in desired amounts to a fuel oil that has emulsified as a result of water having become admixed therewith or may be added to a fuel oil to suppress emulsification thereof when such oils are subsequently exposed to conditions promoting emulsification by admixture of water therewith. For such purposes, the demulsifiers of the present invention may be employed per se, in mixtures thereof, or in combination with a suitable vehicle e.g., a petroleum fraction, to form a concentrated solution or dispersion for addition to the fuels to be treated. For example, when it is desired to add the demulsifying agent in the form of a concentrated solution or dispersion, it is preferably that such a solution or dispersion be prepared by employing a vehicle that is compatible with and does not deleteriously affect the performance of the petroleum distillate fuel to be treated. Hence, particularly suitable vehicles for preparing concentrated solutions or dispersions of the demulsifying agents include petroleum fractions similar to or identical to the petroleum distillate fuel to be treated in accordance with this invention.
In illustration, such concentrates may comprise a petroleum distillate or other suitable liquid hydrocarbon in admixture with a demulsifier as embodied herein and wherein the demulsifier is present in an amount of about 10 to 75% or higher but preferably 10 to 25% based on the weight of the concentrate. As specific illustrations, such concentrates may comprise a suitable hydrocarbon vehicle, e.g., diesel fuels, kerosenes, and other mineral oil fractions, in which there is dissolved or dispersed a demulsifier in amounts varying from about 10 35 to 75% by weight of the concentrate, and, in still more, specific illustration, a suitable concentrate comprising about 50% by Weight of demulsifier in admixture with a petroleum hydrocarbon of diesel fuel grade.
In practice, the general procedure is either to add the '36 process for preventing; resolving or separating emulsions of the oil-in-water class. Emulsions'of the oil-in-water class comprise organic oily materials, which, although immiscible with water or aqueous or non-oily media, are distributed or discompound of our invention at the refinery or at the loadpersed as small drops throughout a continuous body of ing dock using a proportional pump. The pumping dcnon-oily medium. The proportion of dispersed oily mavice adds the product so that it is entirely mixed and thus terial is in many and possibly most cases a minor one. insures that the cargo oil meets all the required specifica- Oil-field emulsions containing small proportions of tions on arrival. crude petroleum oil relatively stably dispersed in water The amount of active emulsion preventive added Will or brine are representative oil-in-water emulsions. Other vary depending upon many factors, for example, the fuel oil-in-water emulsions include: steam cylinder emulsions, oil, the amount of agitation encountered, the amount of in which traces 'of lubricating oil are'found dispersed in water, etc. In most cases suitable results are obtained condensed steam from steam engines and steam pumps, employing 0.005 to 2 parts of active compound per 100 wax-hexane-water emulsions, encountered in de-waxing parts of oil, but preferably 0.01 to 1 part per 100 parts operations in oil refining; butadiene tar-in-water emulof oil. In certain oils, the lower concentrations are sions, encountered in the manufacture of butadiene from satisfactory whereas with certain more readily emulsifiheavy naphtha by cracking in gas generators, and 00- able oils, the higher concentrations are desirable. cur-ring particularly in the wash box Waters of such sys- In order further to describe this phase of our inventerns; emulsions of flux oi in steam condensate protion, several of the test compositions are prepared by disduced in the catalytic dehydrogenation of butylene to solving 0.2% of the following compounds of this invenproduce b-utadiene; styrene-in-water emulsions in syntion in a diesel fuel, mixing the thus prepared solution thetic rubber plants; synthetic latex-in-water emulsions, with an equal amount of either distilled water or synfound in plants producing copolymer butadiene-styrene thetic sea water, and subjecting the resulting admixtures or GRS synthetic rubber; oil-in-water emulsions occurto stirring at the rate of 1500 revolutions per minute. ring in the cooling Water systems of gasoline absorption Blanks are prepared by mixing the diesel fuel with displants; pipe press emulsions from steam-actuated presses tilled water or synthetic sea water in equal amounts. in clay pipe manufacture; emulsions of petroleum resi- The test compositions containing no demulsifier form dues-in-diethylene glycol, in the dehydration of natural emulsions which persist for long periods of time after gas.
stirring is stopped. Test compositions containing the compounds shown in the following table either do not emulsify or the emulsions are completely resolved within a short time after stirring is stopped.
In other industries and arts, emulsions of oily materials in water or other non-oily media are encountered, for example, in sewage disposal operations, synthetic resin emulsion paint formulation, milk and mayonnaise process- EMULSION PREVENTATIVE FOR OIL IN TRANSIT I II Ex. N0. H O Weight of alkylene oxides added Reactants (grams) elimito I in alphabetical order nated (grams) (grams) 1a (439)+oleic acid (846) 54 (A) PrO (32620) (B)Et0(3690) 1a (439)+0leic acid (846) 54 (A)Pr0(40000) (B;EtO(2300) 1a (439)+oleic acid (846)-. 54 (A)Pr0(40000) (B Et0(871 1a (439)+ole c acid (846)-. 54 (A)Pr0 (48620) (B)EtO(2585) 1a (439)+01e1c acid (846)-- 54 (A)Pr0 (48620) (B)Et0(5560) 1a (489)+oleic acid (846) 54 (A)PrO(48620) (B EtO 32 1a (439)+01eic acid (846) 54 (A)PrO (59830) (B)Et0(15390) 1c (645)-i-1auric acid (600) 54 1c (645)+lauric acid (600) 54 3c (907)+laurie acid (600)- (A) BuO (30880) (B)Et0 (7720) (A) PrO (54520) (B) EtO (20440) (A)B11O (26600) (B) EtO (19120) (A) Pro (17560) (B) EtO (13630) 28a (1960)+1auric acid (600) 28a (1960)+lauric acid (600) 28a0 (3054)+stearic acid (284). 18 28aAO A (A) PrO (47640) (B) EtO (5950) (A)B11O (17040) (B)Et0 (5680) (A)BuO (780) (B) PrO (1264) (C) EtO (7720) 28b (1400)+o1eic acid (564) a 281) (1400)+oleic acid (564) 29b0 (2655)+oleic acid (282) 18 29bAOA (A) Pro (40000 (B )EtO (15000 (A) EtO (1995) (B)Pr0 12000 30b (1580) 30b (l580)+stearic acid (569). 30b (1580)+stearic acid (569) 40 ing, marine ballast water disposal and furniture polish formulation. In cleaning the equipment used in processing such products, diluted oil-in-water emulsions are in- (2) BREAKING OIL-IN-WATER EMULSIONS This phase of our invention relates to the use of the oxyalkllated and other products of this invention in a advertently, incidentally, or accidentally produced. The
disposal of aqueous wastes is, in general, hampered by the presence of oil-in-water emulsions.
Essential oils comprise non-saponifiable materials like terpenes, lactones, and alcohols. They also contain saponifiable esters or mixtures of saponificable and nonsaponifiable materials. Steam distillation and other production procedures sometimes cause oil-in-water emulsions to be produced, from which the valuable essential oils are difficultly recoverable.
In all such examples, a non-aqueous or oily material is emulsified in an aqueous or non-oily material with which it is naturally immiscible. The term oil is used herein to cover broadly the water-immiscible materials present as dispersed particles in such systems. The nonoily phase obviously includes diethylene glycol, aqueous solutions, and other non-oily media in addition to water itself.
The foregoing examples ilustrate the fact that, within the broad genus of oil-in-water emulsions, there are at least three important sub-genera. In these, the dispersed oily material is respectively non-saponifiable, saponifiable, and a mixture of non-saponifiable and saponifiable materials. Among the most important emulsions of non saponifiable material in water are petroleum oil-in-water emulsions. Saponifiable oil-in-Water emulsions have dispersed phases comprising, for example, saponifiahle oils and fats and fatty acids, saponifiable oily or fatty esters, and the organic components of such esters to the extent such components are immiscible with aqueous media. Emulsions produced from certain blended lubricating compositions containing both mineral and fatty oil ingredients are examples of the third sub-genus.
Oil-in-water emulsions contain widely different proportions of dispersed phase. Where the emulsion is a waste product resulting from water flushing of manufacturing areas or equipment, the oil content may be only a few parts per million. Resin emulsion paints, as produced, contain a major proportion of dispersed phase. Naturallyoccurring oil-field emulsions of the oil-in-water class carry crude oil in proportions varying from a few parts per million to about or higher in certain cases.
This phase of the present invention is concerned with the resolution of those emulsions of the oil-in-water class which contain a minor proportion of dispersed phase, ranging, for example, from 20% or higher down to 50 parts per million or less.
Although the present process relates to emulsions containing for example as much as 20% or more dispersed oily material, many if not most of them contain appreciably less than this proportion of dispersed phase. In fact, most of the emulsions encountered in the development of this invention have contained about 1% or less of dispersed phase. It is to such oil-in-water emulsions having dispersed phase volumes of .the order of 1% or less to which the present process is particularly directed. This does not mean that any sharp line of demarcation exists and that, for example, an emulsion containing 1.0% of dispersed phase will respond to the process, whereas one containing 1.1% of the same dispersed phase will remain unafi'ected; but that, in general, dispersed phase proportions of the order of 1% or less appear most favorable for application of the present process.
In emulsions having high proportions of dispersed phase, appreciable amount of some emulsifying agent are probably present, to account for their stability. In the case of more dilute emulsions, containing 1% or less of dispersed phase, there may be difficulty in accounting for their stability on the basis of the presence of an emulsifying agent in the conventional sense. For example, steam condensate frequently contains very small proportions of refined petroleum lubricating oil in extremely stable dispersion; yet neither the steam condensate nor the refined hydrocarbon oil would appear to contain anything suitable to stabilize the emulsion. In such cases, emulsion stability must probably be predictated on some basis other than the presence of an emulsifying agent.
The present process is not believed .to depend for its effectiveness on the application of any simple laws, because it has a high level of effectiveness when used to resolve emulsions of widely different composition, e.g., crude or refined petroleum in water or diethylene glycol, as well as emulsions of oily materials like animal or vegetable oils or synthetic oily materials in water.
Some emulsions are by-products of manufacturing procedures in which the composition of the emulsion is known. In many instances, however, the emulsions to be resolved are either naturally-occurring or are acci dentally or unintentionally produced; or in any event they do not result from a deliberate or premeditated procedure. In numerous instances, the emulsifying agent is unknown and as a matter of fact an emulsifying agent, in the conventional sense, may be felt to be absent. It is obviously very difiicult or even impossible to recommend a resolution procedure for the treatment of such latter emulsions, on the basis of theoretical knowledge. Many of the most important applications of the present process are concerned with the resolution of emulsions which are either naturally-occurring or are accidentally, unintentionally, or unavoidably produced. Such emulsions are commonly of the most dilute type, containing about 1% or less of dispersed phase, although higher concentrations are often encountered.
The process which constitutes this phase of the present invention consists in subjecting an emulsion of the oil-inwater class to the action of a demulsifier of the kind de' scribed, thereby causing the oil particles in the emulsion to coalesce sufficiently to rise to the surface of the nonoily layer (or settle to the bottom, if the oil density is greater) when the mixture is allowed to stand in the quiescent state after treatment with the reagent or demulsifier.
Applicability of the present process can be readily de termined by direct trial on any emulsion, without reference to theoretical considerations. This fact facilitates its application to naturally-occurring emulsions, and to emulsions accidentally, unintentionally, or unavoidably produced; since no laboratory experimentation, to discover the nature of the emulsion components or of the emulsifying agent, is required.
Our reagents are useful in undiluted form or diluted with any suitable solvent. Water is commonly found to be a highly satisfactory solvent, because of its ready availability and negligible cost; but in some cases, nonaqueous solvents such as an aromatic petroleum solvent may be found preferable. The products themselves may exhibit solubilities ranging from rather modest waterdispersibility to full and complete dispersibility in that solvent. Because of the small proportions in which our reagents are customarily employed in practicing our process, apparent solubility in bulk has little significance. In the extremely low concentrations of use they undoubtedly exhibit appreciable water-solubility or water-clispersibility as well as oil-solubility or oil-dispersibility.
Our reagents may be employed alone, or they may in some instances be employed to advantage admixed with other and compatible oil-in-water demulsifiers.
Our process is commonly practiced simply by introducing small proportions of our reagent into an oil-inwater class emulsion, agitating to secure distribution of the reagent and incipient coalescence, and letting stand until the oil phase separates. The proportion of reagent required will vary with the character of the emulsion to be resolved. Ordinarily, proportions of reagent required are from 1/ 10,000 to 1/ 1,000,000 by volume of emulsion treated; but prefereably is 5-50 p.p.m. More reagent is sometimes required. We have found that the factors, reagent feed rate, agitation, and settling time are some what interrelated. For example, we have found that if sufficient agitation or proper character is employed, the
factory results.
flows through a conduit or pipe. In some cases, agitation and mixing are achieved by stirring together or shaking together the emulsion and reagent. In some instances, distinctly improved results are obtained by the use of air or other gaseous medium. Where the volume of gas employed is relatively small and the conditions of its introduction relatively mild, it behaves as a means of securing ordinary agitation. Where aeration is effected by introducing a gas directly under pressure or from porous plates or by means of aeration cells, the effect is often importantly improved. A sub-aeration type flotation cell, of the kind commonly employed in ore beneficiation operations, is an extremely useful adjunct in the application of our reagents to many emulsions. It frequently accelerates the separation of the emulsion, reduces reagent requirements, or produces an improved effluent. Sometimes all three improvements are observable.
Heat is ordinarily of little importance in resolving oilin-water class emulsions with our reagents although there are some instances Where heat is a useful adjunct. This is especially true where the viscosity of the continuous phase of the emulsion is appreciably higher than that of water.
In some instances, importantly improved results are obtained by adjusting the pH of the emulsion to be treated to an experimentally determined optimum value.
The reagent feed rate also has an optimum range, which is sufficiently wide, however, to meet the tolerances required for the variances encountered daily in commercial operations. A large excess of reagent can produce distinctly unfavorable results.
Our reagents have likewise been successfully applied to other oil-in-water class emulsions, of which representative examples have been referred to above. Their use is,
40 therefore, not limited to crude petroleum-in-water emulsions.
The manner of practicing the present invention is clear from the foregoing description. However, for completemess the following example is included:
Example An oil-in-water class emulsion produced from an oil Well in the Coalinga field located in Southern California contains about 1,500 ppm. of crude oil, on the average, and is stable for days in the absence of external resolution. Our process is practiced by flowing the well fluids, comprising free crude oil, oil-in-water emulsion and natural gas, through a gas separator, then to a steel tank of 5,000 barrel capacity. In this tank the oil-in-water emulsionfalls to the bottom and is separated from the free oil. The oil-in-water emulsion is withdrawn from the bottom of the tank and the reagent of Example 2-1 introduced into the stream. The proportion employed is about 5 ppm. based on the volume of emulsion, on the average. The chemicalized emulsion flows to a second tank, mixing being achieved in the pipe. In the second tank it is allowed to stand quiescent. Clear water is withdrawn from the bottom of this tank, separated oil from the top.
The compounds in the following table are tested on oil-in-water emulsions taken from two currently producing oil fields, Coalinga, located in Southern California, and Mt. Poso, located in Southern California, according to the following procedure:
Natural crude oil-in-Water emulsions are subjected to .the demulsifiers set forth below. The'mixture of emulsion 4O demulsification.
OIL-IN-WATER DEMULSIFIER Dernulsi- Ex. No.
Reactants (grams) Weight of alkylene oxide added to I (grams) fication Ratio (p-p- H20 eliminated )+lauric acid a 0 28210 (3054)+stearie acid (284)...
(A) PIO (380) (B) litO (240)..--" EtO (960 (B) PrO (220) EtO (1560) 29b (1635 idleie acid (282) 30b (lfiggg-i-stearic acid (569)..
5 30bAOA
Claims (1)
1. A PROCESS FOR TREATING EMULSIFIABLE MATERIALS IN AN EMULSION FORMING ENVIRONMENT TO RESOLVE ANY PREFORMED EMULSION AND TO PREVENT FORMATION OF EMULSIONS WHICH INCLUDES SUBJECTING THE EMULSIFIABLE MATERIALS INCLUDING ANY PREFORMED EMULSIONS TO THE ACTION OF A TREATING AGENT SELECTED FROM THE GROUP CONSISTING OF: (1) ACYLATED, (2) OXYALKYLATED, (3) ACYLATED THEN OXYALKYLATED, (4) OXYALKYLATED THEN ACYLATED, (5) ACYLATED, THEN OXYALKYLATED AND THEN ACYLATED, MONOMERIC POLYAMINOMETHYL PHENOLS CHARACTERIZED BY REACTING A PREFORMED METHYLOL PHENOL HAVING OUT TO FOUR METHYLOL GROUPS IN THE 2,4,6 POSITION WITH A POLYAMINE CONTAINING AT LEAST ONE SECONDARY AMINE GROUP IN AMOUNTS OF AT LEAST ONE MOLE OF SECONDARY POLYAMINE PER EQUIVALENT OF METHYLOL GROUP ON THE PHENOL UNTIL ONE MOLE OF WATER PER EQUIVLAENT OF METHYLOL GROUP IS REMOVED, IN THE ABSENCE OF AN EXTRANEOUS CATALYST; AND THEN REACTING THE THUS FORMED MONOMERIC POLYAMINOMETHYL PHENOL WITH A MEMBER SELECTED FROM THE GROUP CONSISTING OF (1) AN ACYLATION AGENT, (2) AN OXYALKYLATION AGENT, (3) AN ACYLATION THEN AN OXYALKYLATION AGENT, (4) AN OXYALKYLATION THEN AN ACYLATION AGENT, AND (5) AN ACYLATION THEN AN OXYALKYLATION AND THEN AN ACYLATION AGENT, THE PREFORMED METHYLOL PHENOL HAVING ONLY FUNCTIONAL GROUPS SELECTED FROM THE CLASS CONSISTING OF METHYLOL GROUPS AND PHENOLIC HYDROXYL GROUPS, THE POLYAMINE HAVING ONLY FUNCTIONAL GROUPS SELECTED FROM THE CLASS CONSISTING OF PRIMARY AMINO GROUPS, SECONDARY AMINO GROUPS AND HYDROXYL GROUPS, THE ACYLATION AGENT HAVING UP TO 40 CARBON ATOMS AND BEING SELECTED FROM THE CLASS CONSISTING OF UNSUBSTITUTED CARBOXYLIC ACIDS, UNSUBSTITUTED HYDROXY CARBOXYLIC ACIDS, UNSUBSTITUTED ACYLATED HYDROXY CARBOXYLIC ACIDS, LOWER ALKANOL ESTERS OF UNSUBSTITUTED CARBOXYLIC ACIDS, GLYCERIDES OF UNSUBSTITUTED CARBOXYLIC ACIDS, UNSUBSTITUTED CARBOXYLIC ACID CHLORIDES AND UNSUBSTITUTED CARBOXYLIC ACID ANHYDRIDES, AND THE OXYALKYLATION AGENT BEING SELECTED FROM THE CLASS CONSISTING OF ALPHA-BETA ALKYLENE OXIDES AND STYRENE OXIDE.
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US28514A US3148154A (en) | 1960-05-12 | 1960-05-12 | Prevention and/or resolution of emulsions |
US101627A US3060210A (en) | 1960-05-12 | 1961-04-10 | Polyaminomethyl phenols |
US101629A US3096190A (en) | 1960-05-12 | 1961-04-10 | Bituminous compositions containing methylol phenol derivatives |
US102093A US3148150A (en) | 1960-05-12 | 1961-04-11 | Process for preventing, reducing and removing hard-water scale employing methylol pheol derivatives |
US102091A US3056498A (en) | 1960-05-12 | 1961-04-11 | Froth flotation process employing polyamino methyl phenols |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US28514A US3148154A (en) | 1960-05-12 | 1960-05-12 | Prevention and/or resolution of emulsions |
Publications (1)
Publication Number | Publication Date |
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US3148154A true US3148154A (en) | 1964-09-08 |
Family
ID=21843876
Family Applications (1)
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US28514A Expired - Lifetime US3148154A (en) | 1960-05-12 | 1960-05-12 | Prevention and/or resolution of emulsions |
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